JP2002049113A - Silver halide photographic emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sliver halide emulsion less liable to a change in the spectral absorption intensity of the emulsion with a multilayer-adsorbed sensitizing dye and having enhanced stability to a dispersion of a coupler in oil. SOLUTION: In the silver halide photographic emulsion containing silver halide grains having the spectral absorption maximum at <500 nm wavelength and a light absorption intensity of >=60 or the spectral absorption maximum at >=500 nm wavelength and a light absorption intensity of >=100, a sensitizing dye has been added in a form other than a solution of the dye in an organic solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a spectrally sensitized silver halide photographic emulsion and a photographic light-sensitive material using the same.

[0002]

2. Description of the Related Art Hitherto, great efforts have been made to increase the sensitivity of silver halide photographic light-sensitive materials (light-sensitive materials). In a silver halide photographic emulsion, a sensitizing dye adsorbed on the surface of a silver halide grain absorbs light incident on a photographic material, and transmits light energy to the silver halide grain, thereby obtaining photosensitivity. Therefore, in the spectral sensitization of silver halide, the light energy transmitted to the silver halide can be increased by increasing the light absorptivity per unit grain surface area of the silver halide grains, thereby increasing the spectral sensitivity. It is believed that sensitivity is achieved. In order to improve the light absorptance on the surface of silver halide grains,
What is necessary is just to increase the adsorption amount of the spectral sensitizing dye per unit particle surface area. However, the amount of the sensitizing dye adsorbed on the surface of the silver halide grain is limited, and the monolayer saturated adsorption (ie, 1
It is difficult to adsorb more dye chromophores than layer adsorption. Therefore, at present, the absorptance of the incident light quantum of each silver halide grain in the spectral sensitization region is still low.

A method proposed to solve these points is described below. P.B. Gilman, Jr. et al., Photographic Science and Engine Nearing (Photographic Science and).
Engineering, Vol. 20, No. 3, No. 97 (1976), a cationic dye was adsorbed on the first layer, and an anionic dye was adsorbed on the second layer using electrostatic force. GB Bird et al., In U.S. Pat. No. 3,622,316, adsorb multiple dyes onto silver halide in multiple layers and apply them to Forster (Ford).
sensitized by the contribution of the (ster) type excitation energy transfer.

Sugimoto et al., JP-A-63-138,341.
Nos. 64-84 and 244, spectral sensitization was performed by energy transfer from the luminescent dye. R. Steiger et al., Photographic Science and Engine Nearing (Photographic Science and)
Engineering, Vol. 27, No. 2, No. 59, 1983 (1983), an attempt was made to spectrally sensitize a gelatin-substituted cyanine dye by energy transfer. Conducted spectral sensitization by energy transfer from a cyclodextrin-substituted dye in JP-A-61-251842. Also, Richard Parton et al., European Patent 0985964A1, European Patent 0985965A1, European Patent 0985966A1, European Patent 0988565A.
In No. 1, multilayer adsorption was performed using a combination of a cationic dye and an anionic dye, and an attempt was made to increase the sensitivity by transferring energy from the second-layer dye to the first-layer dye.

However, in these methods, the degree to which the sensitizing dye is adsorbed in multiple layers on the surface of the silver halide grains is actually insufficient, and the effect of improving the sensitivity is extremely small. Yamashita et al. In Japanese Patent Application Laid-Open No. 10-239789 have realized multi-layer adsorption using a cationic dye having an aromatic group and an anionic dye to increase the sensitivity. However, the interaction between the second-layer dye and the first-layer dye that are not directly adsorbed on silver halide is weak, and when the emulsion is left for a long time in a state where the emulsion is dissolved, the second-layer dye is desorbed, The absorption based on that changes. In the production process, it is necessary to store the emulsion in a dissolved state before applying the emulsion to which the sensitizing dye has been adsorbed. Therefore, the sensitizing dye multilayer-adsorbed emulsion has been required to be able to maintain absorption and other properties in a state of being dissolved for a long time without causing a change in absorption due to desorption of the second-layer dye. In the color light-sensitive material, various compounds such as a color coupler are added in the form of an emulsified dispersion of an organic solvent. Therefore, there is often a problem that the dye adsorbed on the surface of the silver halide grains is taken in oil droplets of the organic solvent contained in the emulsified dispersion and is desorbed to reduce the light absorption intensity. The multilayer adsorptive dye on the surface of silver halide grains in a color light-sensitive material is required to have such a property that its absorption intensity is hard to change with respect to the emulsified dispersion. Therefore, there has been a need for a technique for realizing dye multilayer adsorption in which the light absorption intensity is stably maintained with respect to the emulsified dispersion.

On the other hand, sensitizing dyes are added in various forms in order to make the sensitizing dyes adsorb on the surface of silver halide grains. For example, a method of dissolving in a water-affinity organic solvent and adding it in the form of a solution is considered to be general as disclosed in JP-B-49-46416, but since a large amount of organic solvent is used, this method is used. Is not preferable from the viewpoint of safety or environmental impact. Therefore, there has been a demand for a technique for adding a multilayer adsorption dye to an emulsion without using a large amount of an organic solvent.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to add a sensitizing dye without using a large amount of an organic solvent and obtain a highly stable and highly sensitive halogen such that the spectral absorption of the sensitizing dye does not change. An object of the present invention is to provide a silver halide photographic emulsion and a photographic light-sensitive material using the same.

[0008]

Means for Solving the Problems (1) Silver halide grains having a spectral absorption maximum wavelength of less than 500 nm and a light absorption intensity of 60 or more, or a spectral absorption maximum wavelength of 500 nm or more and a light absorption intensity of 100 or more are contained. A silver halide photographic emulsion, characterized in that a sensitizing dye is added in a form other than a solution using an organic solvent. (2) The silver halide photographic emulsion according to (1), wherein the sensitizing dye is added in the form of a solid fine dispersion. (3) The silver halide emulsion according to (2), wherein the sensitizing dye is added in the form of a solid fine dispersion in which the sensitizing dye is finely dispersed using a surfactant. (4) The sensitizing dye is added in the form of an oil droplet dispersion in which a solution of the sensitizing dye is finely dispersed in water (1).
A silver halide photographic emulsion as described above. (5) The silver halide photographic emulsion according to (4), wherein the sensitizing dye is added in the form of an oil droplet dispersion in which the sensitizing dye is finely dispersed using a surfactant. (6) The content of the solvent used for dissolving the sensitizing dye is 5
% Or less, the silver halide photographic emulsion according to (4) or (5). (7) The silver halide photographic emulsion according to (2), (3), (4), (5) or (6), wherein gelatin is used as a dispersion medium. (8) A silver halide photographic emulsion in which a sensitizing dye is multi-layer-adsorbed on the surface of silver halide grains, (1), (2), (3), (4), (5) ), (6) or (7). (9) When the maximum value of the spectral absorption by the sensitizing dye is Amax, the wavelength interval between the shortest wavelength and the longest wavelength that indicates 50% of Amax is 120 nm or less (1).
The silver halide photographic emulsion according to (2), (3), (4), (5), (6), (7) or (8). (10) When the maximum value of the spectral sensitivity by the sensitizing dye is Smax, the wavelength interval between the shortest wavelength and the longest wavelength that indicates 50% of Smax is 120 nm or less (1).
The silver halide photographic emulsion according to (2), (3), (4), (5), (6), (7) or (8). (11) The longest wavelength showing a spectral absorption of 50% of Amax is from 460 nm to 510 nm, or from 560 nm to 61.
The silver halide photographic emulsion according to (9) or (10), wherein the emulsion has a thickness of 0 nm or a range of 640 nm to 730 nm. (12) The longest wavelength showing a spectral sensitivity of 50% of Smax is 4
60 nm to 510 nm, or 560 nm to 610
The silver halide photographic emulsion according to (9), (10) or (11), which has a range of from 640 nm to 730 nm. (13) The silver halide photographic emulsion contains a dye having at least one aromatic group (1),
(2), (3), (4), (5), (6), (7),
(8) The silver halide photographic emulsion according to (9), (10), (11) or (12). (14) A sensitizing dye having a basic nucleus fused with three or more rings, (1), (2), (3),
(4), (5), (6), (7), (8), (9),
(10) The silver halide photographic emulsion according to (11), (12) or (13). (15) An emulsion wherein tabular grains having an aspect ratio of 2 or more are present in an amount of 50% (area) or more of all silver halide grains in the emulsion (1), (2), (3),
(4), (5), (6), (7), (8), (9),
(10), (11), (12), (13) or (1)
The silver halide photographic emulsion according to 4). (16) Selenium sensitized (1), (2), (3), (4), (5), (6),
(7), (8), (9), (10), (11), (1
2) The silver halide photographic emulsion according to (13), (14) or (15). (17) (1), (2), (3), which comprises a silver halide-adsorbing compound other than the sensitizing dye.
(4), (5), (6), (7), (8), (9),
(10), (11), (12), (13), (14),
The silver halide photographic emulsion according to (15) or (16). (18) The excitation energy of the second-layer dye is changed to the first-layer dye,
(8), (9), (10), (11), (12), (1)
3) The silver halide photographic emulsion according to (14), (15), (16) or (17). (19) Both the first-layer dye and the second-layer dye exhibit J-band absorption (8), (9), (10),
(11), (12), (13), (14), (15),
(16) The silver halide photographic emulsion according to (17) or (18). (20) (1), (2), (3), (4), which has at least one silver halide photographic emulsion.
(5), (6), (7), (8), (9), (10),
(11), (12), (13), (14), (15),
(16) The silver halide photographic material as described in (17) or (18) or (19).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The present invention relates to a silver halide photographic material using silver halide grains sensitized by a dye that has been multilayer-adsorbed without using a large amount of an organic solvent which requires environmental measures as an additive solvent. The light absorption intensity of the sensitizing dye does not change with respect to additives such as, and the effect of stably maintaining the high sensitivity can be obtained.

In the present invention, the light absorption intensity is the light absorption area intensity by the sensitizing dye per unit particle surface area,
The optical density Log when the amount of light incident on the unit surface area of the particles is I ₀ and the amount of light absorbed by the sensitizing dye on the surface is I.
(I ₀ / (I ₀ −I)) is defined as a value obtained by integrating the wave number (cm ⁻¹ ). Integration range from 5000 cm ^-1 to 35
Up to 000 cm ^-1 .

The silver halide photographic emulsion according to the present invention has a light absorption intensity of 100 or more and a spectral absorption maximum wavelength of 500 in the case of grains having a spectral absorption maximum wavelength of 500 nm or more.
In the case of grains having a particle diameter of less than nm, it is preferable that the silver halide grains having a light absorption intensity of 60 or more include at least 1/2 of the total projected area of the silver halide grains. Further, the spectral absorption maximum wavelength is 50
In the case of particles of 0 nm or more, the light absorption intensity is preferably 150 or more, more preferably 170 or more, and particularly preferably 200 or more, and the spectral absorption maximum wavelength is 500 n.
m, the light absorption intensity is preferably 90
Or more, more preferably 100 or more, particularly preferably 1
20 or more. There is no particular upper limit, but preferably 200
0 or less, more preferably 1000 or less, particularly preferably 500 or less. Also, the spectral absorption maximum wavelength is 500n
m for particles less than 350 m.
It is preferably at least nm.

As an example of a method for measuring the light absorption intensity,
Can use a microspectrophotometer.
You. Microspectrophotometer measures the absorption spectrum of a small area
Device that can measure the transmission spectrum of a single particle.
Noh. Of the absorption spectrum of one particle by microspectroscopy
For the measurement, see Yamashita et al.'S report (The Photographic Society of Japan, 199
6th Annual Meeting Abstracts, p. 15)
Can be. From this absorption spectrum, the absorption per particle
Although light intensity is required, the light passing through the particles is
Absorbed on two sides of the surface
Absorption intensity per particle obtained by the method described above.
It can be obtained as の of the yield strength. At this time,
The interval for integrating the absorption spectrum is
5000cm ^-1From 35000cm^-1But on the experiment
Is 500 cm before and after the section with absorption by the sensitizing dye^-1About
It may be the integral of the section including the degree. Also, the light absorption intensity increases.
The strength of the dye and the number of adsorbed molecules per unit area
These values are determined uniquely, and the oscillator strength and color of the sensitizing dye
Converted to light absorption intensity by calculating the amount of element adsorbed and particle surface area
You can do it. The oscillator strength of the sensitizing dye is
Solution area intensity (optical density x cm^-1Value proportional to
Can be obtained experimentally as
The absorption area intensity of the dye is A (optical density × cm^-1), Sensitizing color
B (mol / mol Ag) and particle surface area
C (m^Two / MolAg), the light absorption is given by the following equation:
The strength can be determined within an error range of about 10%. 0.156 × A × B / C Even if the light absorption intensity is calculated from this equation, it is based on the above-mentioned definition.
The light absorption intensity (Log (I₀ / (I₀ −
I))) is the wave number (cm^-1) And real)
The same value is obtained.

The sensitizing dye of the present invention (the same applies to other sensitizing dyes and supersensitizers) can be directly dispersed in an emulsion. These can be first dissolved in a suitable solvent, for example, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof, and added to the emulsion in the form of a solution. It is not preferable to use a large amount of the organic solvent from the viewpoint of safety or environmental measures. At this time, bases and acids,
Additives such as surfactants may also be present. Also, ultrasonic waves can be used for dissolution. The sensitizing dye of the present invention is added to an emulsion in a form substantially free of an organic solvent. In the present invention, the solubility of the sensitizing dye in water in the form of fine particles having a diameter of 10 μm or less in water is obtained by mechanically grinding the sensitizing dye substantially insoluble in water.
A dispersion dispersed at a concentration of 5 times or more is called a fine solid dispersion. Substantially insoluble in water means that the solubility in water is 0.1% by weight
The following cases are said. The diameter of the fine particles dispersed in water can be measured from an optical microscope or a pattern obtained by diffracting and scattering light emitted from a laser light source by the fine particles. The sensitizing dye substantially insoluble in water is preferably added in the form of a solid fine dispersion. In order to mechanically pulverize the sensitizing dye in water, various dispersers are effectively used. Specifically, a high-speed stirrer, a ball mill, a sand mill, a colloid mill, an attritor, an ultrasonic disperser, or the like is used. When mechanically refining the sensitizing dye in water, a surfactant may be used. The temperature at which the sensitizing dye is dispersed in water is in the range of 0 ° C to 100 ° C, preferably in the range of 20 ° C to 80 ° C, more preferably 40 ° C.
The temperature ranges from ℃ to 80 ℃. The dispersion of the sensitizing dye is mixed with a water-soluble polymer to provide sedimentation resistance, for example,
Long-term storage or refrigeration at temperatures below 30 ° C is possible. The water-soluble polymer used in the present invention is a linear polymer compound having a molecular weight of 1,000 or more, which is soluble in water at room temperature at 0.5% by weight or more, and specifically, gelatin, carboxymethyl cellulose, hydroxyethyl cellulose,
Examples include cellulose sulfate, chondroitin sulfate, sodium alginate, chitin, chitosan, polyvinyl alcohol, polyethylene glycol, polypropylene glycol, sodium polyacrylate, polyvinylpyrrolidone, and copolymers thereof.
Gelatin and polyvinyl alcohol are preferred, and gelatin is more preferred. In the present invention, a water-soluble polymer may be used alone, or a plurality of water-soluble polymers may be used in combination. These water-soluble polymers may be added as an aqueous solution or as a solid. When adding a water-soluble polymer, a known preservative can be used as necessary. The concentration of these water-soluble polymers used as a dispersion medium in water is 0.
It is preferably at least 5% by weight, more preferably at least 1% by weight.
0% by weight or less, more preferably 2% by weight or more and 10% by weight or less.
% By weight or less. Since the mixed composition is prepared using the water-soluble polymer in this manner, the prepared sensitizing dye dispersion can be stably stored for a long period of one month or more simply by cooling without performing drying or the like. became. The sensitizing dye, which is substantially insoluble in water, is dissolved in a small amount of an organic solvent, and the concentrated solution is mixed and stirred in water to a diameter of 10%.
A dispersion dispersed as microscopic oil droplets having a size of micrometer or less is called an oil droplet dispersion. The diameter of the micro oil droplets dispersed in water can be measured from an optical microscope or a pattern obtained by diffracting and scattering light emitted from a laser light source by the micro oil droplets. It is also preferable to add a sensitizing dye substantially insoluble in water to the emulsion as a fine oil droplet dispersion. Any organic solvent for dissolving the sensitizing dye may be used, specifically, benzene,
Toluene, xylene, benzyl alcohol, phenethyl alcohol, pyridine, phenoxyethanol and the like can be mentioned, preferably benzyl alcohol, phenethyl alcohol and phenoxyethanol, more preferably benzyl alcohol and phenoxyethanol. To disperse a concentrated solution of sensitizing dye in water,
Various dispersers are effectively used. Specifically, a high-speed stirrer, an attritor, an ultrasonic disperser, or the like is used.
When the oil droplets of the concentrated solution of the sensitizing dye are refined in water, a surfactant may be used. The temperature at which the concentrated solution of the sensitizing dye is dispersed in water is in the range of 0 ° C to 100 ° C, preferably in the range of 20 ° C to 80 ° C, and more preferably in the range of 40 ° C to 80 ° C. . The oil droplet dispersion of the sensitizing dye can be mixed with a water-soluble polymer to impart sedimentation resistance, and can be stored for a long time at a temperature of, for example, 30 ° C. or refrigerated. The water-soluble polymer used in the present invention is a water-soluble polymer having a molecular weight of 100
0 or more linear polymer compounds, specifically, gelatin, carboxymethylcellulose, hydroxyethylcellulose, cellulose sulfate, chondroitin sulfate, sodium alginate, chitin, chitosan, polyvinyl alcohol, polyethylene glycol, polypropylene glycol, polyacrylic acid Sodium, polyvinylpyrrolidone, and the like, and copolymers thereof, and the like. Gelatin and polyvinyl alcohol are preferred, and gelatin is more preferred. In the present invention, a water-soluble polymer may be used alone, or a plurality of water-soluble polymers may be used in combination. These water-soluble polymers may be added as an aqueous solution or as a solid. When adding a water-soluble polymer, a known preservative can be used as necessary.
The concentration of these water-soluble polymers in water is preferably 0.5% by weight or more, more preferably 1% by weight or more and 50% by weight or less, and further preferably 2% by weight or more and 10% by weight or less. When the oil droplet dispersion of the sensitizing dye is added to the emulsion, the content of the organic solvent used relative to the total amount of the emulsion and the dispersion is preferably 0.1% or more and 5% or less, more preferably
It is 0.2% or more and 4% or less, more preferably 0.3% or more and 3% or less, and most preferably 0.4% or more and 2% or less. Since the mixed composition is prepared using the water-soluble polymer in this manner, the prepared sensitizing dye oil droplet dispersion can be stably stored for a long period of one month or more simply by cooling without performing drying or the like. It became so. Methods for increasing the light absorption intensity include a method of adsorbing more than one layer of the dye chromophore on the particle surface, a method of increasing the molecular extinction coefficient of the dye, and a method of reducing the dye occupied area. May be used, but a method is preferred in which more than one layer of the dye chromophore is adsorbed on the particle surface. Here, the state where more than one layer of the dye chromophore is adsorbed on the grain surface means that more than one layer of the dye bound in the vicinity of the silver halide grain is present, and the dye existing in the dispersion medium Not included. In so-called multilayer adsorption, in which one or more layers of dye chromophores are adsorbed on the surface of a grain, it is necessary that spectral sensitization is caused by a dye that is not directly adsorbed on the grain surface. It is necessary to transfer the excitation energy from the undyed dye to the dye directly adsorbed on the particles. Therefore, if the transmission of the excitation energy needs to occur in more than 10 steps, the final transmission efficiency of the excitation energy is undesirably low. One example of this is the case where most of the dye chromophore is present in the dispersion medium, such as a polymer dye as disclosed in JP-A-2-113239, and transmission of excitation energy is required in 10 or more steps. In the present invention, the number of dye coloring stages per molecule is preferably from 1 to 3, more preferably from 1 to 2.

The chromophore described herein means an atomic group that is the main cause of the absorption band of the molecule described in the Dictionary of Physical and Chemical Sciences (4th edition, Iwanami Shoten, 1987), pp.985-986. Any atomic group is possible, such as an atomic group having an unsaturated bond such as C = C and N = N.

For example, cyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, rhodacyanine dyes, complex cyanine dyes, complex merocyanine dyes, allopolar dyes, oxonol dyes, hemioxonol dyes, squarium Dye, croconium dye,
Azamethine dye, coumarin dye, arylidene dye, anthraquinone dye, triphenylmethane dye, azo dye, azomethine dye, spiro compound, metallocene dye,
Fluorenone dye, fulgide dye, perylene dye, phenazine dye, phenothiazine dye, quinone dye, indigo dye, diphenylmethane dye, polyene dye, acridine dye, acridinone dye, diphenylamine dye,
Examples include quinacridone dyes, quinophthalone dyes, phenoxazine dyes, phthaloperylene dyes, porphyrin dyes, chlorophyll dyes, phthalocyanine dyes, and metal complex dyes. Preferably, cyanine dye, styryl dye, hemicyanine dye, merocyanine dye, trinuclear merocyanine dye, tetranuclear merocyanine dye, rhodacyanine dye, complex cyanine dye, complex merocyanine dye, allopolar dye, oxonol dye, hemioxonol dye, squarium dye, Croconium dye,
And polymethine chromophores such as azamethine dyes.
More preferably, a cyanine dye, a merocyanine dye, or 3
Nuclear merocyanine dyes, tetranuclear merocyanine dyes and rhodacyanine dyes, particularly preferred are cyanine dyes, merocyanine dyes and rhodacyanine dyes, and most preferred are cyanine dyes.

For details of these dyes, see FM Harmer, "Heterocyclic Compounds-Cyanine Soybeans and Related.
Compounds (Heterocyclic Compounds-Cyanine Dyes a
nd Related Compounds), John Wiley & Sons, Inc.-New York, London, 1964, DM Sturmer (DMStu
rmer), Heterocyclic Compounds-Special topics in heterocyclic chemistry
terocyclic chemistry) ", Chapter 18, Section 14, Section 4
82-515. Preferred general formulas of the dyes include general formulas described in U.S. Pat. No. 5,994,051 at pages 32 to 36 and U.S. Pat.
7, 236, pp. 30-34. Also, preferred cyanine dyes, merocyanine dyes,
The general formula for rhodacyanine dyes is described in US Pat.
No. 694, columns 21-22 (XI), (XII) and (XIII) (however, the number of n12, n15, n17 and n18 is not limited, and is an integer of 0 or more (preferably 4 or more). Below)).

The adsorption of the dye chromophore to the silver halide grains is preferably at least 1.5 layers, more preferably 1.7 layers.
More than two layers, particularly preferably two or more layers. Although there is no particular upper limit, the number is preferably 10 or less, more preferably 5 or less.

The meanings of the terms used in the present invention are described below. Dye occupied area: occupied area per dye molecule. It can be determined experimentally from the adsorption isotherm. In the case of a dye in which a dye chromophore is linked by a covalent bond, the dye occupied area of each dye in a non-linked state is used as a reference. 80 for simplicity
A ^2. Single-layer saturated coating amount: The amount of dye adsorbed per unit particle surface area at the time of one-layer saturated coating. Reciprocal of the smallest dye occupied area among the added dyes. Multilayer adsorption: A state in which the amount of dye chromophore adsorbed per unit particle surface area is larger than the one-layer saturation coverage. Number of adsorbed layers: the amount of dye chromophore adsorbed per unit particle surface area based on the saturated coating amount per layer.

In the present invention, the state in which more than one layer of chromophore is adsorbed on the surface of silver halide grains, ie, the state of multilayer adsorption, means that among the sensitizing dyes added to the emulsion, the dye occupation on the surface of silver halide grains. The saturated adsorption amount per unit surface area reached by the dye having the smallest area is defined as one-layer saturated coverage, and the amount of dye chromophore adsorbed per unit area is larger than the one-layer saturated coverage. The number of adsorbed layers means the amount of adsorption based on the one-layer saturated coverage.
Here, in the case of a dye in which a dye chromophore is linked by a covalent bond, the dye occupied area of each dye in a non-linked state can be used as a reference. The dye occupied area can be determined from an adsorption isotherm showing the relationship between the free dye concentration and the amount of adsorbed dye, and the particle surface area. Adsorption isotherms are described, for example, by A. Herz et al. In Adsorption from Aquaeas Solutions.
n from Aqueous Solution) Advances in Chemistry Series (Adv
ances in Chemistry Series
s) No. 17 and 173 (1968).

The amount of the sensitizing dye adsorbed on the emulsion grains is determined by separating the emulsion adsorbed with the dye into a centrifugal separator to separate the emulsion grains and the supernatant gelatin aqueous solution, and measuring the unadsorbed dye concentration by measuring the spectral absorption of the supernatant. Subtracting from the amount of dye added to determine the amount of adsorbed dye, and drying the precipitated emulsion particles, dissolving a certain weight of the precipitate in a 1: 1 mixture of aqueous sodium thiosulfate and methanol, and performing spectral absorption measurement Can be used to determine the amount of adsorbed dye. When a plurality of types of sensitizing dyes are used, the adsorption amount of each dye can be determined by a technique such as high performance liquid chromatography. A method for determining the amount of dye adsorbed by quantifying the amount of dye in the supernatant is described in, for example, Journal of Physical Chemistry (W. West) et al.
Physical Chemistry) Vol. 56, 1
054 (1952). However, under conditions where the amount of dye added is large, even unadsorbed dye may precipitate, and the method of quantifying the dye concentration in the supernatant may not always obtain the correct amount of dye. On the other hand, if the method of measuring the amount of dye adsorbed by dissolving the precipitated silver halide particles, the emulsion particles have an overwhelmingly high sedimentation speed, so that the particles and the sedimented dye can be easily separated, and the dye adsorbed on the particles Only the quantity can be measured accurately. This method is the most reliable as a method for obtaining the dye adsorption amount. The amount of the photographically useful compound adsorbed on the particles can be measured in the same manner as the sensitizing dye. However, since the absorption is small in the visible light region, a quantitative method by high performance liquid chromatography is preferable to a quantitative method by spectral absorption.

As an example of a method for measuring the surface area of a silver halide grain, there is a method in which a transmission electron micrograph is taken by a replica method and the shape and size of each grain are obtained and calculated. In this case, the thickness of the tabular grains is calculated from the length of the shadow of the replica. Examples of a method for taking a transmission electron micrograph include, for example, “Electron Microscope Sample Techniques” edited by the Kanto Chapter of the Electron Microscopy Society of Japan, Seikodo Shinkosha 19
70th edition, Butterworth (Butterworth)
s), London, 1965, PB Hirsch et al., Electron Microscope of Chin Crystal (Electron).
Microscopy of ThinCrysta
ls).

Other methods are described, for example, in the journal of AM Kragin et al.
Of Photographic Science (The Jo
urnal of Photographic Sci
ence, Vol. 14, p. 185 (1966), Transactions of the Fara, JF Paddy's Transactions of the Faraday-Society
day Society, Vol. 60, page 1325 (1
964), S. Boyer et al., Journal de Chimie Ph.
ysique et de Physicochimi
e biologice, Vol. 63, p. 1123 (1963), W. Wes
t) et al. of Journal of Physical Chemistry
Istry) Volume 56, 1054 pages (1952)
), H. Sauvenie
r) Editing, E. Klein et al. International Colloquium (International)
al Coloquium), Liege (Lieg)
e), 1959, "Scientific Photograph.
hy)) can be referred to. The dye occupation area can be determined experimentally for each case by the above method, but the molecular occupation area of a commonly used sensitizing dye is approximately 80%.
Since in the vicinity Å ^2, simply all of the dye can also be estimated roughly the number of adsorption layers a dye occupation area as 80 Å ² for.

The shortest value which shows 50% each of the maximum value Amax of the spectral absorption by the sensitizing dye and the maximum value Smax of the spectral sensitivity of the emulsion containing silver halide photographic emulsion grains having a light absorption intensity of 60 or 100 or more. The interval between the wavelength and the longest wavelength is preferably 120 nm or less, more preferably 100 nm or less. 80% of Amax and Smax
The interval between the shortest wavelength and the longest wavelength indicating
It is at least 100 nm, preferably at most 100 nm, more preferably at most 80 nm, particularly preferably at most 50 nm. Further, the interval between the shortest wavelength and the longest wavelength which represent 20% of Amax and Smax is preferably 180 nm or less, more preferably 150 nm or less, and particularly preferably 120 nm.
Or less, most preferably 100 nm or less. The longest wavelength showing a spectral absorption of 50% of Amax or Smax is preferably 460 nm to 510 nm, or 560 nm to 610 nm, or 640 nm to 730 nm.

In the present invention, when the dye chromophore is adsorbed on the silver halide grains in multiple layers, the dye chromophore of the first layer and the dye of the second or higher layer directly adsorbed on the silver halide grains. The reduction potential and oxidation potential of the chromophore may be any, but the reduction potential of the dye chromophore of the first layer is 2 or less.
It is preferable that the noble metal is nobler than the value obtained by subtracting 0.2 v from the value of the reduction potential of the dye chromophore of the layer or higher.

Although various methods can be used for measuring the reduction potential and the oxidation potential, preferably, the measurement is performed by phase discrimination type second harmonic AC polarography, and accurate values can be obtained. . The method for measuring the potential by the phase discrimination type second harmonic AC polarography is described in Journal of Imaging Science (Journ).
al of Imaging Science), 3rd
0, page 27 (1986).

The dye chromophore of the second or higher layer is preferably a luminescent dye. As the kind of the luminescent dye, those having a skeleton structure of a dye used for a dye laser are preferable. These are described, for example, by Mitsuo Maeda, Laser Research, Vol. 8, pp. 694, 803, 958 (1980) and Vol. 9, p. 85 (1981), and F. Sehaefer.
Author, "Dye Lasers", Springer (1973).

Further, it is preferable that the maximum absorption wavelength of the dye chromophore of the first layer in the silver halide photographic light-sensitive material is longer than the maximum absorption wavelength of the dye chromophore of the second layer or more. Further, it is preferable that the emission of the dye chromophore of the second layer or more overlaps with the absorption of the dye chromophore of the first layer. Also,
The dye chromophore in the first layer preferably forms a J-aggregate. Further, in order to have absorption and spectral sensitivity in a desired wavelength range, it is preferable that the dye chromophores of the second layer or more also form J-aggregates. The energy transfer efficiency of the excitation energy of the second-layer dye to the first-layer dye is preferably 30% or more, more preferably 60%, and particularly preferably 90% or more. The efficiency of energy transfer from the second-layer dye to the first-layer dye can be determined as spectral sensitization efficiency when the second-layer dye is excited / spectral sensitization efficiency when the first-layer dye is excited.

In order to enhance the interaction between the first-layer dye and the second-layer dye, electrostatic interaction, van der Waals interaction, hydrogen bonding, and It is preferable to utilize site bonds and their complex interaction forces. Further, the main interaction between the dyes in the second layer is preferably van der Waals interaction between the dye chromophores, but as long as the above preferable relationship is satisfied, electrostatic interaction, Van der Waals interaction, hydrogen bonding It is also preferred to utilize coordination bonds and their complex interactions. 1 for the total adsorption energy of the second layer dye
Although it is difficult to actually determine the ratio of the interaction energy between the dyes in the second layer and the second layer, it can be estimated by using a computer chemistry technique such as a molecular force field calculation. Further, experimentally, the aggregation energies of the second-layer dye molecules and the first-layer dye molecules and the second-layer dye molecules were measured, and 100
× Cohesive energy of first-layer dye and second-layer dye molecules / (2
It can also be estimated as (the cohesive energy between the dye molecules of the first layer and the dye molecules of the first and second layers). The cohesive energy can be determined, for example, using the method of Matsubara and Tanaka et al. (Journal of the Photographic Society of Japan, 52: 395, 1989).

The maximum spectral absorption wavelength is less than 500 nm and the light absorption intensity is 60 or more, or the maximum spectral absorption wavelength is 500 n
A preferred first method for realizing silver halide grains having a light absorption intensity of 100 or more and a light absorption intensity of 100 or more is a method using the following specific dye.

For example, Japanese Patent Application Laid-Open Nos. 10-239789 and 8
-269,092 and 10-123650, JP-A-8-
Dyes having an aromatic group described in 328189;
A method using a combination of a cationic dye having an aromatic group and an anionic dye; a method using a dye having a multivalent charge described in JP-A-10-171588;
A method using a dye having a pyridinium group described in No. 4774, a method using a dye having a hydrophobic group described in JP-A-10-186559,
197980, a method using a dye having a coordination bonding group, and Japanese Patent Application Nos. 11-63588, 11
-80141, 11-159731, 11-1
No. 59730, No. 11-171324, No. 11-22
No. 1479, No. 11-265768, No. 11-260
No. 643, No. 11-331571, No. 11-3315
No. 70, No. 11-311039, No. 11-33156
7, No. 11-3477781, Japanese Patent Application No. 2000-189.
A method using a specific dye described in No. 66 is preferable.

A particularly preferred method is a method using a dye having at least one aromatic group. Among them, preferably a positively charged dye, a dye whose charge is offset in the molecule, or a method using only a dye having no charge, or a combination of positive and negatively charged dyes, and positive and negative In this method, at least one of the charged dyes uses a dye having at least one aromatic group as a substituent.

The aromatic group will be described in detail. Examples of the aromatic group include a hydrocarbon aromatic group and a heteroaromatic group. These are groups having a polycyclic fused ring in which hydrocarbon aromatic rings and heteroaromatic rings are fused together, or a polycyclic fused ring structure in which an aromatic hydrocarbon ring and an aromatic heterocyclic ring are combined, And may be substituted with a substituent V described below. As the aromatic ring contained in the aromatic group, preferably, benzene, naphthalene, anthracene, phenanthrene, fluorene, triphenylene, naphthacene, biphenyl, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyridine, pyrazine,
Pyrimidine, pyridazine, indolizine, indole,
Benzofuran, benzothiophene, isobenzofuran,
Examples include quinolidine, quinoline, phthalazine, naphthyridine, quinoxaline, quinoxazoline, quinoline, carbazole, phenanthridine, acridine, phenanthroline, thianthrene, chromene, xanthene, phenoxatiin, phenothiazine, phenazine and the like.

More preferably, it is the above-mentioned hydrocarbon aromatic ring, particularly preferably benzene or naphthalene, and most preferably benzene.

Examples of the dye include those described above as examples of the dye chromophore. Preferably, the dyes mentioned as examples of the polymethine dye chromophore described above are used.

More preferably, cyanine dye, styryl dye, hemicyanine dye, merocyanine dye, trinuclear merocyanine dye, tetranuclear merocyanine dye, rhodocyanine dye, complex cyanine dye, complex merocyanine dye, allopolar dye, oxonol dye, hemioxonol dye , Squarium dye, croconium dye, azamethine dye, more preferably cyanine dye, merocyanine dye, trinuclear merocyanine dye, tetranuclear merocyanine dye, rhodacyanine dye,
Particularly preferred are cyanine dyes, merocyanine dyes and rhodacyanine dyes, and most preferred are cyanine dyes.

Particularly preferred methods will be described in detail with reference to structural formulas.

That is, the following cases (1) and (2) are preferable. In (1) and (2), (2) is more preferable. (1) A method using at least one of cationic, betaine, and nonionic methine dyes represented by the following general formula (I). (2) A method in which at least one of the cationic methine dyes represented by the following general formula (I) and at least one of the anionic methine dyes represented by the following general formula (II) are simultaneously used. General formula (I)

[0038]

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In the formula, Z ₁ represents an atom group necessary for forming a nitrogen-containing heterocyclic ring. However, the rings may be condensed with these. R ₁ is an alkyl group, an aryl group, or a heterocyclic group. Q ₁ represents a group necessary for the compound represented by the general formula (I) to form a methine dye. L ₁ and L ₂ represent a methine group. p ₁ represents 0 or 1. Where Z
₁ , R ₁ , Q ₁ , L ₁ , and L ₂ have a substituent in which the methine dye represented by the general formula (I) as a whole becomes a cationic dye, a betaine dye, or a nonionic dye.
However, when the general formula (I) is a cyanine dye or rhodacyanine dye, it preferably has a substituent that becomes a cationic dye. M ₁ represents a counter ion for charge balancing, and m ₁ represents a number of 0 or more necessary to neutralize the charge of the molecule. General formula (II)

[0040]

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In the formula, Z ₂ represents an atom group necessary for forming a nitrogen-containing heterocyclic ring. However, the rings may be condensed with these. R ₂ is an alkyl group, an aryl group, or a heterocyclic group. Q ₂ represents a group necessary for the compound represented by formula (II) to form a methine dye. L ₃ and L ₄ represent a methine group. p ₂ represents 0 or 1. Where Z
₂ , R ₂ , Q ₂ , L ₃ and L ₄ have a substituent in which the methine dye represented by the general formula (II) as a whole becomes an anion dye. M ₂ represents a counter ion for charge balancing, and m ₂ represents a number of 0 or more necessary to neutralize the charge of the molecule.

However, when the compound of the formula (I) is used alone, R ₁ is preferably a group having an aromatic ring.

Further, the compound of the general formula (I) and the compound of the general formula (II)
When the compound of the formula ( ₁ ) is used in combination, at least one of R ₁ and R ₂ is preferably a group having an aromatic ring. More preferably, both R ₁ and R ₂ are groups having an aromatic ring.

The cationic dye of the present invention may be any dye in which the charge of the dye excluding the counter ion is cationic, but is preferably a dye having no anionic substituent. The anionic dye of the present invention may be any dye having an anionic charge except for a counter ion, but is preferably a dye having at least one anionic substituent. The betaine dye of the present invention is a dye that has a charge in the molecule but forms an intramolecular salt, and the molecule has no charge as a whole. With the nonionic dye of the present invention,
A dye that has no charge in the molecule.

The term "anionic substituent" as used herein refers to a substituent having a negative charge, for example, a proton dissociable acidic group dissociated by 90% or more at a pH of 5 to 8. Specifically, for example, a sulfo group, a carboxyl group, a sulfato group,
And a phosphate group and a borate group. In addition, -CO
NHSO ₂ - group (sulfonylcarbamoyl group, a carbonyl sulfamoyl group), - CONHCO- group (carbonylation carbamoyl group), - SO ₂ NHSO ₂ - group (sulfonylsulfamoyl group), a phenolic hydroxyl group, etc., these pka And a group at which the proton is dissociated depending on the surrounding pH. More preferably a sulfo group, a carboxyl group, -CONHSO ₂ - group, -CON
HCO- group, -SO ₂ NHSO ₂ - a group. Note that -C
ONHSO ₂ — group, —CONHCO— group, —SO ₂ NH
In some cases, the SO ₂ — group does not dissociate a proton due to its pka and surrounding pH. In this case, the SO ₂ — group is not included in the anionic substituent herein. That is, when the proton is not dissociated, for example, even if two of these groups are substituted for a dye represented by the following general formula (I-1),
It can be considered as a cationic dye. Examples of the cationic substituent include a substituted or unsubstituted ammonium group and a pyridinium group.

The dye represented by the general formula (I) is more preferably represented by the following general formulas (I-1), (I-2) and (I-3). General formula (I-1)

[0047]

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In the general formula (I-1), L ₅ , L ₆ , L ₇ , L
₈ , L ₉ , L ₁₀ and L ₁₁ represent a methine group. p ₃ and p ₄ represent 0 or 1. n ₁ represents 0, ₁ , 2, 3 or 4. Z ₃ and Z ₄ represent an atom group necessary for forming a nitrogen-containing heterocyclic ring. However, the rings may be condensed with these. R ₃ and R ₄ are an alkyl group, an aryl group,
Or a heterocyclic group. M ₁ and m ₁ have the same meanings as in formula (I). However, R ₃ , R ₄ , Z ₃ , Z ₄ , L _{5 to} L ₁₁ are
When (I-1) is a cationic dye, it has no anionic substituent, and when (I-1) is a betaine dye, it has one anionic substituent.

Formula (I-2)

[0050]

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In the formula (I-2), L₁₂, L₁₃, L₁₄, And L_Fifteen
Represents a methine group. p_Five Represents 0 or 1. q₁ Is 0 or
Represents 1. n_TwoRepresents 0, 1, 2, 3 or 4. Z_Five 
Represents an atom group necessary for forming a nitrogen-containing heterocyclic ring.
Z₆ And Z₆’Is (N-R₆) q₁ Together with a heterocycle,
Represents the group of atoms necessary to form an acyclic acidic end group.
Represent. Where Z_Five , And Z₆ And Z₆Is fused to the ring
May be. R_Five And R₆ Is an alkyl group, an aryl group,
Or a heterocyclic group. M₁ , M₁ Is synonymous with general formula (I)
is there. Where R_Five , R₆ , Z_Five , Z₆ , L₁₂~ L_FifteenIs
When (I-2) is a cationic dye, it has a cationic substituent
In the case where (I-2) is a betaine dye, the cationic substituent 1
And one has an anionic substituent, and (I-2) is a nonionic
In the case of dyes, a cationic substituent and an anionic substituent
do not have. General formula (I-3)

[0052]

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In the formula (I-3), L₁₆, L₁₇, L₁₈, L₁₉, L
₂₀, L_{twenty one}, L_{twenty two}, L_{twenty three}, And L_{twenty four}Represents a methine group. p
₆ And p₇ Represents 0 or 1. q_Two Represents 0 or 1.
n_ThreeAnd n_Four Represents 0, 1, 2, 3 or 4. Z₇ ,
And Z₉ Is the group of atoms necessary to form a nitrogen-containing heterocycle.
Represent. Z₈ And Z₈’Is (N-R₈) q_Two Together with
Represents the group of atoms necessary to form a ring. Where Z
₇ , Z₈ And Z₈’And Z₉ Even if the ring is fused
good. R₇ , R₈ And R₉ Is an alkyl group, an aryl group,
Or a heterocyclic group. M₁ , M₁ Is synonymous with general formula (I)
is there. Where R ₇ , R₈ , R₉ , Z₇ , Z₈ , Z₉ , L
₁₆~ L_{twenty four}Is anionic when (I-3) is a cationic dye
When there is no substituent and (I-3) is a betaine dye,
It has one sex substituent.

Further, as the anionic dye represented by the general formula (II), more preferably, the following general formula (II-1):
This is the time represented by (II-2) and (II-3). General formula (II-1)

[0055]

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In the general formula (II-1), L ₂₅ , L ₂₆ , L ₂₇ , L
₂₈ , L ₂₉ , L ₃₀ and L ₃₁ represent a methine group. p ₈ and p ₉ represent 0 or 1. n ₅ represents 0, 1, 2, 3 or 4. Z ₁₀ and Z ₁₁ represent an atomic group necessary for forming a nitrogen-containing heterocyclic ring. However, the rings may be condensed with these. R ₁₀ and R ₁₁ are an alkyl group, an aryl group,
Or a heterocyclic group. M ₂ and m ₂ have the same meanings as in formula (II). However, R ₁₀ and R ₁₁ have an anionic substituent.

Formula (II-2)

[0058]

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In the formula (II-2), L₃₂, L₃₃, L₃₄, And L
₃₅Represents a methine group. p₉ Represents 0 or 1. q_Three Is 0
Or represents 1. n₆ Represents 0, 1, 2, 3 or 4. Z
₁₂Represents the atoms required to form a nitrogen-containing heterocyclic ring.
You. Z₁₃And Z₁₃’Is (N-R₁₃) Q_Three Together with
Necessary to form an aromatic or acyclic acidic end group
Represents an atomic group. Where Z₁₂, And Z₁₃And Z₁₃’With a ring
It may be annulated. R ₁₂And R₁₃Is an alkyl group, ant
A heterocyclic group or a heterocyclic group. M_Two , M_Two Is the general formula (I
Synonymous with I). Where R₁₂, R₁₃At least
One has an anionic substituent. General formula (II-3)

[0060]

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In the formula (II-3), L₃₆, L₃₇, L₃₈, L₃₉,
L₄₀, L₄₁, L₄₂, L₄₃, And L₄₄Represents a methine group.
p_TenAnd p₁₁Represents 0 or 1. q_Four Represents 0 or 1
You. n ₇ And n₈ Represents 0, 1, 2, 3 or 4.
Z₁₄, And Z₁₆Is necessary to form a nitrogen-containing heterocycle
Represents an atomic group. Z_FifteenAnd Z_Fifteen’Is (N-R_Fifteen) Q_FourWith
Represents a group of atoms necessary to form a heterocyclic ring.
Where Z₁₄, Z_FifteenAnd Z_Fifteen’, And Z₁₆Has a ring fused
May be. R₁₄, R_FifteenAnd R₁₆Is an alkyl group,
Represents a reel group or a heterocyclic group. M_Two , M_Two Is the general formula
Synonymous with (II). Where R₁₄, R_Fifteen, R₁₆Out of
At least two have anionic substituents.

However, when the compounds of the general formulas (I-1), (I-2) and (I-3) are used alone, at least one, preferably both of R ₃ and R ₄ are aromatic rings. group having, R ₅
And at least one of R ₆ , preferably a group having an aromatic ring, and at least one, preferably two, and more preferably at least three of R ₇ , R ₈ , and R _9. A group having

When the compounds of the general formulas (I-1), (I-2) and (I-3) are used in combination with the compounds of the general formulas (II-1), (II-2) and (II-3) Represents R _{3 to} R ₉ , and R ₁₀ to
At least one of R ₁₆ is a group having an aromatic ring, preferably two are groups having an aromatic ring, more preferably three are groups having an aromatic ring, and particularly preferably four The above is the group having an aromatic ring.

According to the preferred method described above, the spectral absorption maximum wavelength is less than 500 nm and the light absorption intensity is 60 or more, or the spectral absorption maximum wavelength is 500 nm or more and the light absorption intensity is 10 or more.
Although silver halide grains of 0 or more can be realized,
Since the dye in the second layer is usually adsorbed in a monomer state, it is almost always wider than the desired absorption width and spectral sensitivity width. Therefore, in order to realize high sensitivity in a desired wavelength region, it is necessary to form a J-aggregate in the dye adsorbed in the second layer. Furthermore, since the J-aggregate has a high fluorescence yield and a small Stokes shift, it is also necessary to transfer the light energy absorbed by the second-layer dye to the first-layer dye having a close light absorption wavelength by Forster-type energy transfer. preferable.

In the present invention, the dye of the second layer or more is
A dye adsorbed on silver halide grains but not directly adsorbed on silver halide. In the present invention, the J-aggregate of the dye in the second layer or more is defined as a monomer in a monomer state having no interaction between the dye chromophores, in which the absorption width of the dye adsorbed in the second layer or more is on the long wavelength side. It is defined as not more than twice the absorption width of the long wavelength side of the absorption exhibited by the dye solution. Here, the absorption width on the long wavelength side indicates an energy width between an absorption maximum wavelength and a wavelength that is longer than the absorption maximum wavelength and exhibits an absorption of 1/2 of the absorption maximum. It is generally known that when a J-aggregate is formed, the absorption width on the longer wavelength side becomes smaller than that in the monomer state. When adsorbed to the second layer in the monomer state,
Due to the non-uniformity of the adsorption position and the state, the absorption width becomes twice or more the absorption width on the long wavelength side in the monomer state of the dye solution.
Therefore, a J-aggregate of the dye in the second or higher layer can be defined by the above definition.

The spectral absorption of the dye adsorbed on the second or more layers is
It can be determined by subtracting the spectral absorption of the first layer dye from the total spectral absorption of the emulsion. The spectral absorption by the first-layer dye can be determined by measuring the absorption spectrum when only the first-layer dye is added. Further, by adding a dye desorbing agent to the emulsion in which the sensitizing dye is adsorbed in multiple layers to desorb the dyes in the second or more layers, the spectral absorption spectrum of the dye in the first layer can be measured. In an experiment in which a dye is desorbed from the particle surface using a dye desorbing agent, the first layer dye is usually desorbed after the second or more layers of dye have been desorbed. Spectral absorption can be determined. This makes it possible to determine the spectral absorption of the dyes in the second and higher layers. The method using a pigment desorbing agent
Report of Asanuma et al. (Journal of Physical Chemistry B)
Chemistry B), Vol. 101, pp. 2149 to 2153 (1997)).

To form a J-aggregate of the second-layer dye using a cationic dye, a betaine dye, or a nonionic dye represented by the general formula (I) and an anionic dye represented by the general formula (II) The dye to be adsorbed as the first layer and 2
It is preferable to separate and add the dye to be adsorbed to the layers after the first layer, and it is more preferable to use dyes having different structures for the first-layer dye and the second-layer or higher dye. It is preferable to add a cationic dye, a betaine dye, or a nonionic dye alone or a combination of a cationic dye and an anionic dye to the second or higher layer dye.

As the dye for the first layer, any dye can be used. Preferably, the dyes of the general formula (I) or (I)
The dye represented by I), more preferably the dye represented by the general formula (I). As the second layer dye, it is preferable to use the cationic dye, the betaine dye, or the nonionic dye of the general formula (I) alone. In the case where a cationic dye and an anionic dye are used in combination as the preferred second layer dye in the same row, it is preferable that one of the two is a cationic dye of the general formula (I) or an anionic dye of the general formula (II), Further, it is preferable to include both the cationic dye of the general formula (I) and the anionic dye of the general formula (II). The ratio of the cationic dye / anionic dye as the second layer dye is preferably from 0.5 to 2, more preferably from 0.75 to 1.33, and most preferably from 0.9 to 1.
11 range.

In the present invention, a dye other than the dye represented by the general formula (I) or (II) may be added.
The dye represented by the general formula (I) or (II) is preferably at least 50%, more preferably at least 70%, most preferably at least 90% of the total amount of the dye added.
By adding the second-layer dye in this manner, the interaction between the second-layer dyes can be enhanced while promoting the rearrangement of the second-layer dyes, so that a J-aggregate can be formed.

When the dye of the general formula (I) or the general formula (II) is used as the first layer dye, Z
₁ and Z ₂ are preferably a basic nucleus substituted with an aromatic group or a basic nucleus condensed with three or more rings. When used as a second or higher layer dye, Z ₁ and Z ₂ are preferably basic nuclei condensed with three or more rings.

The number of condensed rings of the basic nucleus is, for example, 2 for the benzoxazole nucleus and 3 for the naphthoxazole nucleus. Even when the benzoxazole nucleus is substituted with a phenyl group, the number of condensed rings is 2. The basic nucleus condensed with three or more rings is not particularly limited as long as it is a polycyclic condensed heterocyclic basic nucleus condensed with three or more rings.
Cyclic condensed heterocyclic rings and tetracyclic condensed heterocyclic rings are included. As the tricyclic condensed heterocyclic ring, naphtho [2,3-
d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,1-d] oxazole, naphtho [2,3-d] thiazole,
Naphtho [1,2-d] thiazole, naphtho [2,1-d] thiazole, naphtho [2,3-d] imidazole, naphtho [1,2-d] imidazole, naphtho [2,1-d] imidazole, Naft [2,3-
d] selenazole, naphtho [1,2-d] selenazole, naphtho [2,1-d] selenazole, indolo [5,6-d] oxazole, indolo [6,5-d] oxazole, indolo [2,3- d]
Oxazole, indolo [5,6-d] thiazole, indolo
[6,5-d] thiazole, indolo [2,3-d] thiazole, benzofuro [5,6-d] oxazole, benzofuro [6,5-d] oxazole, benzofuro [2,3-d] oxazole, benzofuro [5,6-d] thiazole, benzofuro [6,5-d] thiazole, benzofuro [2,3-d] thiazole, benzothieno [5,6
-d] oxazole, benzothieno [6,5-d] oxazole, benzothieno [2,3-d] oxazole and the like. Further, as the tetracyclic fused ring heterocycle, preferably anthra [2,3-d] oxazole, anthra [1,2-d] oxazole, anthra [2,1-d] oxazole, anthra [2,3-
d] Thiazole, anthra [1,2-d] thiazole, phenanthro [2,1-d] thiazole, phenanthro [2,3-d] imidazole, anthra [1,2-d] imidazole, anthra
[2,1-d] imidazole, anthra [2,3-d] selenazole, phenanthro [1,2-d] selenazole, phenanthro
[2,1-d] selenazole, carbazolo [2,3-d] oxazole, carbazolo [3,2-d] oxazole, dibenzofuro
[2,3-d] oxazole, dibenzofuro [3,2-d] oxazole, carbazolo [2,3-d] thiazole, carbazolo [3,2
-d] Thiazole, dibenzofuro [2,3-d] thiazole, dibenzofuro [3,2-d] thiazole, benzofuro [5,6-d] oxazole, dibenzothieno [2,3-d] oxazole, dibenzothieno [3,2] -d] oxazole, tetrahydrocarbazolo [6,7-d] oxazole, tetrahydrocarbazolo
[7,6-d] oxazole, dibenzothieno [2,3-d] thiazole, dibenzothieno [3,2-d] thiazole, tetrahydrocarbazolo [6,7-d] thiazole and the like. More preferably, the basic nucleus fused with three or more rings is naphtho.
[2,3-d] oxazole, naphtho [1,2-d] oxazole,
Naphtho [2,1-d] oxazole, naphtho [2,3-d] thiazole, naphtho [1,2-d] thiazole, naphtho [2,1-d] thiazole, indolo [5,6-d] oxazole, Indro [6,5-
d] oxazole, indolo [2,3-d] oxazole, indolo [5,6-d] thiazole, indolo [2,3-d] thiazole, benzofuro [5,6-d] oxazole, benzofuro [6,5
-d] oxazole, benzofuro [2,3-d] oxazole,
Benzofuro [5,6-d] thiazole, benzofuro [2,3-d] thiazole, benzothieno [5,6-d] oxazole, anthra
[2,3-d] oxazole, anthra [1,2-d] oxazole, anthra [2,3-d] thiazole, anthra [1,2-d] thiazole, carbazolo [2,3-d] oxazole, carbazolo [3,2-d] oxazole, dibenzofuro [2,3-d] oxazole, dibenzofuro [3,2-d] oxazole, carbazolo [2,3-d] thiazole, carbazolo [3,2-d] thiazole, dibenzofuro [2,3-d] thiazole, dibenzofuro
[3,2-d] thiazole, dibenzothieno [2,3-d] oxazole, dibenzothieno [3,2-d] oxazole, and particularly preferably naphtho [2,3-d] oxazole and naphtho [1 , 2-d] oxazole, naphtho [2,3-d] thiazole, indolo [5,6-d] oxazole, indolo [6,5-d]
Oxazole, indolo [5,6-d] thiazole, benzofuro [5,6-d] oxazole, benzofuro [5,6-d] thiazole, benzofuro [2,3-d] thiazole, benzothieno [5,6]
-d] oxazole, carbazolo [2,3-d] oxazole,
Carbazolo [3,2-d] oxazole, dibenzofuro [2,3-d]
Oxazole, dibenzofuro [3,2-d] oxazole,
Carbazolo [2,3-d] thiazole, carbazolo [3,2-d] thiazole, dibenzofuro [2,3-d] thiazole, dibenzofuro [3,2-d] thiazole, dibenzothieno [2,3-d] oxazole, Dibenzothieno [3,2-d] oxazole.

Hereinafter, the general formula (I) (including (I-1,2,3)),
The methine compound represented by (II) (including (II-1,2,3)) will be described in detail.

In the general formulas (I) and (II), Q ₁ and Q ₂
Represents a group necessary for forming a methine dye. Although any methine dye can be formed by Q ₁ and Q ₂ , the methine dye shown as an example of the aforementioned dye chromophore can be used.

Preferred are cyanine dyes, merocyanine dyes, rhodacyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, allopolar dyes, hemicyanine dyes and styryl dyes. More preferred are cyanine dyes, merocyanine dyes and rhodacyanine dyes, and particularly preferred are cyanine dyes. For more information on these dyes, see FM Harme
r), Heterocyclic Compounds-Cyanine Soybeans and Related Compounds (Heterocyc
lic Compounds-Cyanine Dyes and Related Compound
s) ", John Wiley and Sons
&amp; Sons), New York, London, 1964, DMSturmer, Heterocyclic Compound Special Topics in Heterocyclic Chemistry (Heterocyc)
lic Compounds-Special topics in heterocyclic chemi
stry) ", Chapter 18, Section 14, 482-515. Preferred general formulas of the dyes include the general formulas described in U.S. Pat. No. 5,994,051 at pages 32 to 36, and U.S. Pat.
General formulas described on pages 0 to 34 are exemplified. The general formulas of preferred cyanine dyes, merocyanine dyes and rhodacyanine dyes are described in US Pat. No. 5,340,694, Nos. 21 and 2.
(XI), (XII), and (XIII) in column 2 (however, the number of n12, n15, n17, and n18 is not limited;
Or more integers (preferably 4 or less). In the general formulas (I) and (II), when a cyanine dye or rhodacyanine dye is formed by Q ₁ and Q _2, it can be represented by the following resonance formula. General formula (I)

[0075]

Embedded image

Formula (II)

[0077]

Embedded image

In the general formulas (I) and (II), Z ₁ , Z
_{2, Z 3, Z 4,} Z 5, Z 7, Z 9, Z 10, Z 11,
Z ₁₂ , Z ₁₄ and Z _{16 each} represent a nitrogen-containing heterocyclic ring, preferably 5
Alternatively, it represents an atom group necessary for forming a 6-membered nitrogen-containing heterocyclic ring. However, the rings may be condensed with these. The ring may be either an aromatic ring or a non-aromatic ring. Preferable is an aromatic ring, for example, a hydrocarbon aromatic ring such as a benzene ring and a naphthalene ring, and a heteroaromatic ring such as a pyrazine ring and a thiophene ring.

Examples of the nitrogen-containing heterocycle include thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, oxazoline nucleus, oxazole nucleus, benzoxazole nucleus, selenazoline nucleus,
Selenazole nucleus, benzoselenazole nucleus, 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine), imidazoline nucleus, imidazole nucleus, benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-
Quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3
-Isoquinoline nucleus, imidazo [4,5-b] quinoxaline nucleus, oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus, pyrimidine nucleus and the like,
Preferably, a benzothiazole nucleus, a benzoxazole nucleus, a 3,3-dialkylindolenine nucleus (for example, 3,3
-Dimethylindolenine), benzimidazole nucleus, 2
-Pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-
A quinoline nucleus, a 1-isoquinoline nucleus and a 3-isoquinoline nucleus, more preferably a benzothiazole nucleus, a benzoxazole nucleus, a 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine), and a benzimidazole nucleus. Particularly preferred are a benzoxazole nucleus, a benzothiazole nucleus and a benzimidazole nucleus, and most preferred are a benzoxazole nucleus and a benzothiazole nucleus.

Assuming that the substituent on these nitrogen-containing heterocycles is V, the substituent represented by V is not particularly limited.
For example, a halogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, and a heterocyclic group (also referred to as a heterocyclic group) Good), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group ( Anilino group), an acylamino group, an aminocarbonylamino group,
An alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkyl and arylsulfonylamino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, a sulfo group, an alkyl and arylsulfinyl group, Alkyl and arylsulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups,
Examples include carbamoyl, aryl and heterocyclic azo groups, imide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, and silyl groups. More specifically, V is a halogen atom (eg,
A chlorine atom, a bromine atom, an iodine atom) and an alkyl group [representing a linear, branched, or cyclic substituted or unsubstituted alkyl group; They include an alkyl group (preferably having 1 to 3 carbon atoms).
An alkyl group of 0, for example, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), a cycloalkyl group (preferably having 3 carbon atoms) 30 substituted or unsubstituted cycloalkyl groups such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), bicycloalkyl groups (preferably substituted or unsubstituted bicycloalkyl groups having 5 to 30 carbon atoms, It is a monovalent group obtained by removing one hydrogen atom from bicycloalkane of formulas 5 to 30. For example, bicyclo [1,2,2] heptane-2-yl, bicyclo [2,2,2] octan-3-yl ) And a tricyclo structure having more ring structures. An alkyl group (for example, an alkyl group of an alkylthio group) among the substituents described below also represents an alkyl group having such a concept. And an alkenyl group [which represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They include alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, for example, vinyl, allyl, prenyl,
Geranyl, oleyl), cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a cycloalkene having 3 to 30 carbon atoms) For example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), a bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably having 5 carbon atoms)
To 30 substituted or unsubstituted bicycloalkenyl groups, that is, monovalent groups obtained by removing one hydrogen atom from a bicycloalkene having one double bond. For example, it includes bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2,2] oct-2-en-4-yl). An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms such as ethynyl, propargyl, trimethylsilylethynyl group, an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms) For example, phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound) Is a monovalent group obtained by removing one hydrogen atom from, more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, for example, 2-furyl, 2-thienyl, -Pyrimidinyl, 2-benzothiazolyl), cyano, hydroxyl, nitro, carboxyl, alkoxy (preferably Ku is a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, for example,
Methoxy, ethoxy, isopropoxy, t-butoxy,
n-octyloxy, 2-methoxyethoxy), an aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, phenoxy,
2-methylphenoxy, 4-t-butylphenoxy, 3
-Nitrophenoxy, 2-tetradecanoylaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably carbon A substituted or unsubstituted heterocyclic oxy group of the number 2 to 30, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), an acyloxy group (preferably a formyloxy group, a substituted or unsubstituted group of 2 to 30 carbon atoms) A substituted alkylcarbonyloxy group, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, formyloxy, acetyloxy, pivaloyloxy, stearoyloxy,
Benzoyloxy, p-methoxyphenylcarbonyloxy), carbamoyloxy group (preferably having 1 carbon atom)
To 30 substituted or unsubstituted carbamoyloxy groups, for example, N, N-dimethylcarbamoyloxy,
N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy),
An alkoxycarbonyloxy group (preferably having 2 carbon atoms)
To 30 substituted or unsubstituted alkoxycarbonyloxy groups such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-
Octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyl Oxyphenoxycarbonyloxy), an amino group (preferably,
An amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted anilino group having 6 to 30 carbon atoms, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, Diphenylamino), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, for example, formylamino Acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably having 1 to 3 carbon atoms)
0-substituted or unsubstituted aminocarbonylamino, for example, carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms) A substituted or unsubstituted alkoxycarbonylamino group, for example,
Methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino), aryloxycarbonylamino group (preferably substituted or unsubstituted having 7 to 30 carbon atoms) Aryloxycarbonylamino group, for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino), sulfamoylamino group (preferably having no carbon atoms)
To 30 substituted or unsubstituted sulfamoylamino groups such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably carbon Substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, such as methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-tri Chlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, for example, methylthio, ethylthio, n-hexadecylthio), Ali Lucio group (preferably having a carbon number of 6
To 30 substituted or unsubstituted arylthio, for example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, for example, , 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N- (3
-Dodecyloxypropyl) sulfamoyl, N, N-
Dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- (N'-phenylcarbamoyl) sulfamoyl), sulfo group, alkyl and arylsulfinyl group (preferably having 1 to 30 carbon atoms) Or an unsubstituted alkylsulfinyl group, 6 to 30 substituted or unsubstituted arylsulfinyl groups, for example, methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), alkyl and arylsulfonyl groups (preferably having 1 to 30 substituted or unsubstituted alkylsulfonyl groups, 6 to 30 substituted or unsubstituted arylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl Groups (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, substituted or unsubstituted carbon group having 4 to 30 carbon atoms) A heterocyclic carbonyl group bonded to a carbonyl group by an atom, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl), aryl An oxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-
Nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), alkoxycarbonyl group (preferably substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyl) Oxycarbonyl), carbamoyl group (preferably,
A substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, for example, carbamoyl, N-methylcarbamoyl,
N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms;
A substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, for example, phenylazo, p-chlorophenylazo,
5-ethylthio-1,3,4-thiadiazol-2-ylazo), imide group (preferably N-succinimide, N-phthalimido), phosphino group (preferably
A substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms; For example, phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl), phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, for example, diphenoxyphosphinyl Oxy, dioctyloxyphosphinyloxy), phosphinylamino group (preferably substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino, dimethylaminophosphinylamino ), A silyl group (preferably having 3 carbon atoms) 0 substituted or unsubstituted silyl group, for example, represents trimethylsilyl, t- butyl dimethylsilyl, phenyldimethylsilyl), a.
Also, a ring (aromatic or non-aromatic hydrocarbon ring or heterocyclic ring. These can be further combined to form a polycyclic fused ring. For example, a benzene ring, a naphthalene ring, an anthracene ring, a quinoline ring , A phenanthrene ring,
Fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole ring, benzofuran Ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, quinoline ring, carbazole ring,
Phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, phenothiazine ring, phenazine ring. ) May be condensed.

Among the above functional groups, those having a hydrogen atom may be removed and further substituted with the above group. Examples of such functional groups include alkylcarbonylaminosulfonyl, arylcarbonylaminosulfonyl, alkylsulfonylaminocarbonyl,
An arylsulfonylaminocarbonyl group is exemplified.
Examples include methylsulfonylaminocarbonyl,
p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.

Preferable substituents are the above-mentioned alkyl group, aryl group, alkoxy group, halogen atom, fused aromatic ring, sulfo group, carboxy group and hydroxy group.

Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , Z ₇ , Z
_{9, Z 10, Z 11,} Z 12, Z 14, and more preferably an aromatic group as a substituent V on Z _16, an aromatic ring condensed.

Z ₆ , Z ₆ ′, (NR ₆ ) q ₁ , and Z
₁₃ and Z ₁₃ ′ and (NR ₁₃ ) q ₃ together represent an atom group necessary to form a heterocyclic or acyclic acidic terminal group. The heterocyclic ring (preferably a 5- or 6-membered heterocyclic ring) may be any, but an acidic nucleus is preferred. Next, the acidic nucleus and the acyclic acidic terminal group will be described. The acidic nucleus and acyclic acid end groups can take the form of the acidic nucleus and acyclic acid end groups of any common merocyanine dye. Z in the preferred form
₆ , Z ₁₃ are a thiocarbonyl group, a carbonyl group, an ester group, an acyl group, a carbamoyl group, a cyano group, and a sulfonyl group, and more preferably a thiocarbonyl group and a carbonyl group. Z ₆ ′ and Z ₁₃ ′ represent the remaining atomic groups necessary for forming an acidic nucleus and an acyclic acidic terminal group.
When forming an acyclic acidic terminal group, preferably a thiocarbonyl group, a carbonyl group, an ester group, an acyl group,
A carbamoyl group, a cyano group, a sulfonyl group and the like.

Q ₁ and q ₃ are 0 or 1, but preferably 1.

The acidic nucleus and the acyclic acidic terminal group referred to herein are described, for example, in James, "Theory of the Photographic Process" (The Theory).
Theory of the Photograph
ic Process) 4th edition, Macmillan Publishing Company, 1
977, 198-200. Here, the acyclic acidic terminal group means an acidic or electron-accepting terminal group which does not form a ring. The acidic nucleus and the acyclic acidic end group are, specifically,
U.S. Pat. Nos. 3,567,719, 3,575,86
No. 9, No. 3, 804, 634, No. 3, 837, 862
No. 4,002,480,4,925,777
No. 3,167,546, U.S. Pat.
No. 4,051, U.S. Pat. No. 5,747,236 and the like.

The acidic nucleus forms a heterocycle (preferably a 5- or 6-membered nitrogen-containing heterocycle) consisting of carbon, nitrogen and / or chalcogen (typically oxygen, sulfur, selenium and tellurium) atoms. And more preferably a 5- or 6-membered nitrogen-containing heterocyclic ring composed of carbon, nitrogen and / or chalcogen (typically oxygen, sulfur, selenium and tellurium) atoms. Specifically, for example, the following nuclei can be mentioned.

2-pyrazolin-5-one, pyrazolidin-3,5 dione, imidazoline-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidine-4-one, 2-oxazoline-5-one,
2-thiooxazolidin-2,5-dione, 2-thiooxazoline-2,4 dione, isoxazoline-5-one, 2-thiazoline-4-one, thiazolidine-4-one, thiazolidine-2,4 dione, rhodanine, thiazolidine-2,4-dithione, Isorhodanine, indan-1,3-dione, thiophen-3-one, thiophen-3-one-1,1dioxide, indoline-2
-On, indoline-3-one, 2-oxoindazolinium, 3-oxoindazolinium, 5,7-dioxo6,7 dihydrothiazolo [3,2-a] pyrimidine, cyclohexane-1,3-dione, 3,4 Dihydroisoquinolin-4-one, 1,3-dioxane-4,6 dione, barbituric acid, 2-thiobarbituric acid, chroman-2,4 dione, indazolin-2-one, pyrido [1,2-a] pyrimidine-1,3 dione , Pyrazolo [1,5-b] quinazolone, pyrazolo [1,5-a]
Benzimidazole, pyrazolopyridone, 1, 2, 3,
4-tetrahydroquinoline-2,4-dione, 3-oxo-2,3-dihydrobenzo [d] thiophene-1,1
Dioxide, 3-dicyanomethine-2,3-dihydrobenzo [d] thiophen-1,1-dioxide nucleus.

Further, the carbonyl group or thiocarbonyl group forming these nuclei is substituted at the active methylene position of the acidic nucleus, and the nucleus has an exomethylene structure, and is used as a raw material for an acyclic acidic terminal group. A nucleus having an exomethylene structure substituted at the active methylene position of an active methylene compound having a structure such as ketomethylene or cyanomethylene.

The acidic nucleus and the acyclic acidic terminal group may be substituted or condensed with the substituent or ring represented by the substituent V described above.

Z ₆ and Z ₆ ′ and (NR ₆ ) q ₁ , Z ₁₃ and Z
Preferably ₁₃ ′ and (NR ₁₃ ) q ₃ are hydantoin, 2 or 4-thiohydantoin, 2-oxazoline-5-one, 2-thiooxazoline-2,4dione,
Thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, barbituric acid, 2-thiobarbituric acid, more preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazoline-5-one, rhodanine, barbituric acid 2, 2-thiobarbituric acid. Particularly preferred are 2- or 4-thiohydantoin, 2-oxazolin-5-one, rhodanine and barbituric acid.

Z ₈ and Z ₈ ′ and (N−R ₈ ) q ₂ , Z ₁₅ and Z
_The heterocyclic ring formed by ₁₅ ′ and (N—R ₁₅ ) q ₄ includes the aforementioned Z ₆ and Z ₆ ′, (N—R ₆ ) q ₁ , Z ₁₃ and Z
_The same ones as described in the description of the heterocyclic ring of ₁₃ ′ and (N—R ₁₃ ) q ₃ can be given. Preferably Z ₆ and Z ₆ ′ described above.
And (NR ₆ ) q ₁ , or an acidic nucleus described in the description of the heterocyclic ring of Z ₁₃ and Z ₁₃ ′ and (NR ₁₃ ) q ₃ , from which an oxo group or a thioxo group has been removed.

More preferably, the acid nucleus of the above-mentioned acidic nucleus of Z ₆ and Z ₆ ′ and (N—R ₆ ) q ₁ , Z ₁₃ and Z ₁₃ ′ and (N—R ₁₃ ) q ₃ is oxo. Group or a thioxo group,

More preferably, hydantoin, 2 or 4-thiohydantoin, 2-oxazoline-5-one,
2-thiooxazoline-2,4 dione, thiazolidine-2,4 dione, rhodanine, thiazolidine-2,4
Dithione, barbituric acid, 2-thiobarbituric acid is obtained by removing an oxo group or a thioxo group, particularly preferably, hydantoin, 2 or 4-thiohydantoin, 2-oxazoline-5-one, rhodanine, barbituric acid, Oxo group from 2-thiobarbituric acid,
Or those excluding a thioxo group, most preferably 2
Or 4-thiohydantoin, 2-oxazoline-5-one, or rhodanine from which an oxo group or a thioxo group is removed.

Q ₂ and q ₄ are 0 or 1, but preferably 1.

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R
_{7, R 8, R 9,} R 10, R 11, R 12, R 13, R 14,
R ₁₅ and R ₁₆ are an alkyl group, an aryl group, and a heterocyclic group. Specifically, for example, carbon atoms 1 to 1
8, preferably 1 to 7, particularly preferably 1 to 4, unsubstituted alkyl groups (for example methyl, ethyl, propyl,
Isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), carbon atoms 1 to 18,
Preferably, it is a substituted alkyl group of 1 to 7, particularly preferably 1 to 4, such as an alkyl group substituted by V as a substituent. Preferably an aralkyl group (eg, benzyl, 2-phenylethyl), an unsaturated hydrocarbon group (eg, an allyl group), a hydroxyalkyl group (eg,
2-hydroxyethyl, 3-hydroxypropyl), carboxyalkyl group (for example, 2-carboxyethyl,
3-carboxypropyl, 4-carboxybutyl, carboxymethyl), an alkoxyalkyl group (for example, 2-
Methoxyethyl, 2- (2-methoxyethoxy) ethyl), aryloxyalkyl group (eg, 2-phenoxyethyl, 2- (1-naphthoxy) ethyl), alkoxycarbonylalkyl group (eg, ethoxycarbonylmethyl, 2-benzyloxycarbonylethyl) ), An aryloxycarbonylalkyl group (eg, 3-phenoxycarbonylpropyl), an acyloxyalkyl group (eg,
-Acetyloxyethyl), acylalkyl group (eg, 2-acetylethyl), carbamoylalkyl group (eg, 2-morpholinocarbonylethyl), sulfamoylalkyl group (eg, N, N-dimethylsulfamoylmethyl), sulfoalkyl group (eg, , 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- [3-sulfopropoxy] ethyl, 2-
Hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), sulfoalkenyl group, sulfatoalkyl group (for example, 2-sulfatoethyl group, 3-sulfatopropyl, 4-sulfatobutyl), heterocyclic-substituted alkyl Group (for example, 2- (pyrrolidin-2-one-1)
-Yl) ethyl, tetrahydrofurfuryl), alkylsulfonylcarbamoylalkyl group (eg, methanesulfonylcarbamoylmethyl group), acylcarbamoylalkyl group (eg, acetylcarbamoylmethyl group), acylsulfamoylalkyl group (eg, acetylsulfamoylmethyl group) ), An alkylsulfonylsulfamoylalkyl group (eg, a methanesulfonylsulfamoylmethyl group)}, an unsubstituted aryl group having 6 to 20, preferably 6 to 10, and more preferably 6 to 8 carbon atoms (eg, Phenyl group, 1 naphthyl group),
A substituted aryl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, and more preferably 6 to 8 carbon atoms (for example, an aryl group substituted by V described above as an example of the substituent. Is a p-methoxyphenyl group, p
-Methylphenyl group, p-chlorophenyl group and the like. ), An unsubstituted heterocyclic group having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 4 to 8 carbon atoms (eg, 2-furyl group, 2-thienyl group, 2-pyridyl group, 3-pyrazolyl, 3-iso Oxazolyl, 3-isothiazolyl, 2-imidazolyl, 2-oxazolyl, 2-thiazolyl, 2-pyridyl, 2-pyrimidyl, 3-pyrazyl, 2- (1,3,5-triazolyl), 3- (1,2,4-triazolyl), 5 -Tetrazolyl), a substituted heterocyclic group having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms, and more preferably 4 to 8 carbon atoms (for example, the above-mentioned heterocyclic group substituted by V mentioned as an example of the substituent group) Specific examples include a 5-methyl-2-thienyl group and a 4-methoxy-2-pyridyl group.

R ₁ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R
Preferred as ₈ and R ₉ are groups having an aromatic ring. Examples of the aromatic ring include a hydrocarbon aromatic ring and a heteroaromatic ring, which are furthermore a hydrocarbon aromatic ring and a polycyclic fused ring in which the heteroaromatic rings are fused together, or an aromatic hydrocarbon ring. And a polycyclic fused ring in which is combined with an aromatic heterocyclic ring, and may be substituted with the aforementioned substituent V or the like. As the aromatic ring, those described as examples of the aromatic ring in the above description of the aromatic group are preferable.

The group having an aromatic ring is represented by -Lb-A
It can be represented by ₁ . Here, Lb represents a single bond or a linking group. A ₁ represents an aromatic group. As the linking group for Lb, preferably, the linking group described for La or the like is mentioned. As the aromatic group for A ₁ , those described as examples of the aforementioned aromatic group are preferred.

Preferably, the alkyl group having a hydrocarbon aromatic ring is an aralkyl group (for example, benzyl,
-Phenylethyl, naphthylmethyl, 2- (4-biphenyl) ethyl), an aryloxyalkyl group (for example, 2
-Phenoxyethyl, 2- (1-naphthoxy) ethyl,
2- (4-biphenyloxy) ethyl, 2- (o, m or p-halophenoxy) ethyl, 2- (o, m or p-methoxyphenoxy) ethyl), an aryloxycarbonylalkyl group (3-phenoxycarbonylpropyl, 2- (1-naphthoxycarbonyl) ethyl) and the like. Examples of the alkyl group having a heteroaromatic ring include 2- (2-pyridyl) ethyl and 2- (4-
Pyridyl) ethyl, 2- (2-furyl) ethyl, 2-
(2-thienyl) ethyl and 2- (2-pyridylmethoxy) ethyl are exemplified. 4 as a hydrocarbon aromatic group
-Methoxyphenyl, phenyl, naphthyl, biphenyl and the like. Examples of the heteroaromatic group include a 2-thienyl group, 4-chloro-2-thienyl, 2-pyridyl, and 3-pyrazolyl.

More preferred are the above-mentioned substituted or unsubstituted alkyl groups having a hydrocarbon aromatic ring or a heteroaromatic ring. Particularly preferred are the above-mentioned alkyl groups having a substituted or unsubstituted hydrocarbon aromatic ring.

R ₂ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R
Preferred as ₁₅ and R ₁₆ are groups having an aromatic ring. Both R ₁₀ and R ₁₁ and at least one of R ₁₂ and R ₁₃ and at least one of R ₁₄ , R ₁₅ and R ₁₆ have an anionic substituent. R ₂ preferably has an anionic substituent. Examples of the aromatic ring include a hydrocarbon aromatic ring and a heteroaromatic ring.
Further, it may be a hydrocarbon aromatic ring, a polycyclic fused ring in which heteroaromatic rings are fused together, or a polycyclic fused ring in which an aromatic hydrocarbon ring and an aromatic heterocycle are combined, It may be replaced by V or the like. As the aromatic ring, those described as examples of the aromatic ring in the above description of the aromatic group are preferable.

The group having an aromatic ring is represented by -Lc-A
It can be represented by ₂ . Here, Lc represents a single bond or a linking group. A ₂ represents an aromatic group. As the linking group for Lc, preferably, the linking group described for La or the like is mentioned. The aromatic group for A ₂ is preferably the same as the aforementioned aromatic group. Lc or A ₂ is preferably substituted with at least one anionic substituent.

Preferably, the alkyl group having a hydrocarbon aromatic ring is an aralkyl group substituted by a sulfo group, a phosphate group, or a carboxyl group (eg, 2-sulfobenzyl, 4-sulfobenzyl, 4-sulfophenethyl) , 3-phenyl-3-sulfopropyl, 3-phenyl-2-sulfopropyl, 4,4-diphenyl-3-sulfobutyl, 2- (4'-sulfo-4-biphenyl) ethyl, 4-phosphobenzyl), sulfo Aryloxycarbonylalkyl group (3-sulfophenoxycarbonylpropyl) substituted with a group, a phosphate group or a carboxyl group, an aryloxyalkyl group substituted with a sulfo group, a phosphate group or a carboxyl group (for example, 2- (4-
Sulfophenoxy) ethyl, 2- (2-phosphophenoxy) ethyl, 4,4-diphenoxy-3-sulfobutyl), and the like. Examples of the alkyl group having a heteroaromatic ring include 3- (2-pyridyl) -3-sulfopropyl, 3- (2-furyl) -3-sulfopropyl, and 2- (2-thienyl) -2-sulfopropyl. Propyl and the like. Examples of the hydrocarbon aromatic group include a sulfo group, a phosphoric acid group, and an aryl group substituted with a carboxyl group (eg, 4-sulfophenyl and 4-sulfonaphthyl). Examples of the heteroaromatic group include a sulfo group and a phosphate group. Or a heterocyclic group substituted with a carboxyl group (for example, 4
-Sulfo-2-thienyl group, 4-sulfo-2-pyridyl group) and the like.

More preferred are the above-mentioned alkyl groups having a hydrocarbon aromatic ring or a heteroaromatic ring substituted with a sulfo group, a phosphate group or a carboxyl group. An alkyl group having a hydrocarbon aromatic ring substituted with an acid group or a carboxyl group. Most preferably, 2-sulfobenzyl, 4
-Sulfobenzyl, 4-sulfophenethyl, 3-phenyl-3-sulfopropyl, 4-phenyl-4-sulfobutyl.

L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , L ₆ , L
_{7, L 8, L 9,} L 10, L 11, L 12, L 13, L 14,
_{L 15, L 16, L 17} , L 18, L 19, L 20, L 21, L 22, L
_{23, L 24, L 25,} L 26, L 27, L 28, L 29, L 30,
_{L 31, L 32, L 33} , L 34, L 35, L 36, L 37, L 38, L
_{39, L 40, L 41,} L 42, L 43, and L ₄₄ each independently represents a methine group. The methine group represented by L _{1 to} L ₄₄ may have a substituent, and examples of the substituent include the aforementioned V. For example, a substituted or unsubstituted carbon number of 1 to 1
5, preferably an alkyl group having 1 to 10 carbon atoms, particularly preferably 1 to 5 carbon atoms (eg, methyl, ethyl,
-Carboxyethyl), a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms (eg, phenyl, o-
Carboxyphenyl), a substituted or unsubstituted heterocyclic group having 3 to 20 carbon atoms, preferably 4 to 15 carbon atoms, more preferably 6 to 10 carbon atoms (eg, N, N-dimethylbarbituric acid group), a halogen atom , (Eg, chlorine, bromine, iodine, fluorine), an alkoxy group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (eg, methoxy, ethoxy), 0 to 15 carbon atoms, An amino group having preferably 2 to 10 carbon atoms, more preferably 4 to 10 carbon atoms (eg, methylamino, N,
N-dimethylamino, N-methyl-N-phenylamino, N-methylpiperazino), an alkylthio group having 1 to 15, preferably 1 to 10, more preferably 1 to 5 carbon atoms (eg, methylthio, ethylthio) , Having 6 to 20 carbon atoms, preferably 6 to 1 carbon atoms
2, more preferably an arylthio group having 6 to 10 carbon atoms (eg, phenylthio, p-methylphenylthio) and the like. Further, a ring may be formed with another methine group, or a ring may be formed together with Z _{1 to} Z ₂₅ and R _{1 to} R ₂₅ .

L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , L ₆ , L
_{10, L 11, L 12,} L 13, L 16, L 17, L 23, L 24,
_{L 25, L 26, L 30} , L 31, L 32, L 33, L 36, L 37, L
₄₃ and L ₄₄ are preferably unsubstituted methine groups.

N ₁ , n ₂ , n ₃ , n ₄ , n ₅ , n ₆ , n
₇ and n ₈ each independently represent 0, 1, 2, 3 or 4. It is preferably 0, 1, 2, 3, more preferably 0, 1, 2 and particularly preferably 0, 1. When n ₁ , n ₂ , n ₃ , n ₄ , n ₅ , n ₆ , n ₇ , and n ₈ are 2 or more, the methine group is repeated but need not be the same.

P ₁ , p ₂ , p ₃ , p ₄ , p ₅ , p ₆ , p
₇ , p ₈ , p ₉ , p ₁₀ , and p ₁₁ are each independently 0
Or represents 1. Preferably it is 0.

M ₁ and M ₂ are included in the formula to indicate the presence of a cation or an anion when necessary to neutralize the ionic charge of the dye. Typical cations include inorganic cations such as hydrogen ion (H ⁺ ), alkali metal ions (eg, sodium ion, potassium ion, lithium ion), alkaline earth metal ions (eg, calcium ion), and ammonium ions (eg, Organic ions such as ammonium ion, tetraalkylammonium ion, triethylammonium ion, pyridinium ion, ethylpyridinium ion, and 1,8-diazabicyclo [5.4.0] -7-undecenium ion. The anion may be either an inorganic anion or an organic anion, such as a halogen anion (for example, a fluorine ion, a chloride ion, or an iodine ion), or a substituted arylsulfonate ion (for example, p-ion).
Toluenesulfonic acid ion, p-chlorobenzenesulfonic acid ion), aryldisulfonic acid ion (for example, 1,3-benzenesulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion), alkyl Sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, and trifluoromethanesulfonate ion. Further, another dye having a charge opposite to that of the ionic polymer or the dye may be used. Also, CO
₂ ⁻ and SO ₃ ⁻ can also be expressed as CO ₂ H and SO ₃ H when they have a hydrogen ion as a counter ion.

M ₁ and m ₂ each represent a number of 0 or more necessary to balance the charges, preferably a number of 0 to 4, more preferably a number of 0 to 1, and a salt in the molecule. It is 0 when forming.

Next, only specific examples of the dyes used in the particularly preferred technology described in detail in the description of the embodiments of the invention will be shown below. Of course, the present invention is not limited to these.

Specific examples of the compound represented by the general formula (I) (including the lower conceptual structure) of the present invention.

[0113]

Embedded image

[0114]

Embedded image

Specific examples of the compound represented by the general formula (II) (including the lower conceptual structure) of the present invention.

[0116]

Embedded image

[0117]

Embedded image

The dyes of the present invention are FM Hammer.
(FMHarmer), Heterocyclic Compounds
Cyanine soybeans and related compounds
(Heterocyclic Compounds-Cyanine Dyes and Related C
ompounds) ", John Willy and Sons
n Wiley &amp; Sons)-New York, London, 1
964, DMSturmer, Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry (H
eterocyclic Compounds-Special topics in heterocycl
ic chemistry), Chapter 18, Section 14, 482-515, John Wiley and Sons
ley & Sons)-New York, London, 197
7th year, "Rodd's Chemistry of Carbon Compounds" 2
nd.Ed.vol.IV, partB, 1977, Chapter 15, Chapter 369
422, Elsevier Science Public
Company Inc. (Elsevier Science Publishing Com
pany Inc.), New York, and the above-mentioned patents and literatures (cited for describing specific examples) and the like.

In the present invention, not only the sensitizing dye of the present invention but also other sensitizing dyes other than the present invention may be used or used in combination. Preferred examples of the dye include a cyanine dye, a merocyanine dye, a rhodocyanine dye, a trinuclear merocyanine dye, a tetranuclear merocyanine dye, an allopolar dye, a hemicyanine dye, and a styryl dye. More preferred are cyanine dyes, merocyanine dyes and rhodacyanine dyes, and particularly preferred are cyanine dyes. For more information on these dyes, see FMHarmer, Heterocyclic Compounds-Cyanine Soybeans and Related.
Compounds (Heterocyclic Compounds-Cyanine Dyes a
nd Related Compounds), John Wiley &amp; Sons, Inc.- New York, London, 1964, D.M.
turmer), Heterocyclic Compounds-Special topics in Heterocyclic Compounds-Special topics in
heterocyclic chemistry ", Chapter 18, Section 14, 482-515. Preferred dyes include U.S. Patent No. 5,994,051 32-
No. 44, and U.S. Pat. No. 5,747,236, No. 3,
The sensitizing dyes are shown by the general formulas described on pages 0 to 39 and the specific examples. The general formulas of preferred cyanine dyes, merocyanine dyes and rhodacyanine dyes are described in U.S. Pat. No. 5,340,694, columns 21 to 22, (XI) and (X).
II) and (XIII) (where n12, n1
The number of 5, n17 and n18 is not limited, and is an integer of 0 or more (preferably 4 or less). ).

One of these sensitizing dyes may be used.
Two or more sensitizing dyes may be used, and a combination of sensitizing dyes is often used particularly for supersensitization. Representative examples are U.S. Pat. Nos. 2,688,545 and 2,977,229.
No. 3,397,060 and 3,522,052
No. 3,527,641, No.3,617,293
No. 3,628,964 and 3,666,480
Nos. 3,672,898 and 3,679,428
Nos. 3,303,377 and 3,769,301
No. 3,814,609 and 3,837,862
No. 4,026,707, British Patent 1,344,2
No. 81, No. 1, 507, 803, JP-B-43-493
No. 36, No. 53-12375, JP-A-52-1106
No. 18, No. 52-109925 and the like.

In addition to the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

Supersensitizers useful for spectral sensitization in the present invention (for example, pyrimidylamino compounds, triazinylamino compounds, azolium compounds, aminostyryl compounds, aromatic organic acid formaldehyde condensates, azaindene compounds, cadmium salts) And combinations of supersensitizers and sensitizing dyes are described, for example, in US Pat. No. 3,511,66.
No. 4, No. 3,615,613, No. 3,615,632
Nos. 3,615,641, 4,596,767
Nos. 4,945,038 and 4,965,182
Nos. 4,965,182 and 2,933,390
Nos. 3,635,721 and 3,743,510
Nos. 3,617,295, 3,635,721, etc., and the method described in the above-mentioned patents is also preferable as to the use thereof.

The timing at which the sensitizing dye of the present invention (and other sensitizing dyes and supersensitizers) is added to the silver halide emulsion of the present invention has been found to be useful. During the preparation of the emulsion. For example, US Pat. Nos. 2,735,766 and 3,6
28,960, 4,183,756, 4,22
5,666, JP-A-58-184142, 60-
As disclosed in, for example, Japanese Patent No. 196749, the stage before silver halide grain formation step and / or before desalting, the period during and / or after desalting and before the start of chemical ripening,
As disclosed in JP-A-58-113920 and the like, any time during or immediately before chemical ripening, during the process, or after the chemical ripening and before coating, the emulsion may be added at any time before the coating. May be. Also, U.S. Pat.
As disclosed in US Pat. No. 5,666, JP-A-58-7629, etc., the same compound may be used alone or in combination with a compound having a different structure, for example, during the particle forming step and during the chemical ripening step or during the chemical ripening step. It may be added separately after completion, or before or after chemical ripening or during the process and after completion, and may be added by changing the kind of compound and compound combination to be added separately. May be.

The addition amount of the sensitizing dye of the present invention (the same applies to other sensitizing dyes and supersensitizers) varies depending on the shape and size of silver halide grains. ^Per mol of 1 × 10 ^-6 to 8 × 10 ^-3 mol. For example, when the silver halide grain size is 0.2 to 1.3 μm, the addition amount is preferably 2 × 10 ^{−6 to} 3.5 × 10 ⁻³ mol per mol of silver halide, and is preferably 7.5. An addition amount of from × 10 ^{-6 to} 1.5 × 10 ^-3 mol is more preferable. However, when the sensitizing dye of the present invention is adsorbed in multiple layers as described above, an amount necessary for the multilayer adsorption is added.

In the present invention, examples of the silver halide-adsorbing compound other than the sensitizing dye (a photographically useful compound adsorbed on silver halide grains) include an antifogging agent, a stabilizing agent, a nucleating agent and the like. Antifoggants and stabilizers are described in, for example, Research Disclosure Magazine (Research)
Disclosure) Volume 176 Item 17643
(RD17643), Volume 187, Item 18716 (RD18716)
And the compounds described in Item 308119 (RD308119) of Vol. 308 can be used. Examples of the nucleating agent include, for example, U.S. Pat. Nos. 2,563,785 and 2,582.
Hydrazines described in US Pat.
27,552, hydrazides, hydrazones, British Patent 1,283,835, JP-A-52-696.
13, No. 55-138742, No. 60-11837
No. 62-210451, No. 62-291637
No. 3,615,515 and 3,719,49.
4, 3,734, 738, 4,094,683, 4,115,122, 4306016, 44710
Heterocyclic quaternary salt compounds described in US Pat.
Sensitizing dyes having a substituent having a nucleating effect in a dye molecule described in US Pat. No. 4,030,9;
25, 4,031,127, 4,245,037,
4,255,511, 4,266,013, 4,
276, 364, thiourea-linked acylhydrazine-based compounds described in British Patent 2,012,443 and the like, and US Pat. Nos. 4,080,270 and 4,278,748.
Sialhydrazine-based compounds having a thioamide ring or a heterocyclic group such as triazole or tetrazole and the like as described in British Patent 2,011,391B and the like as an adsorptive group are used.

In the present invention, preferred photographically useful compounds include nitrogen-containing heterocyclic compounds such as thiazole and benzotriazole, mercapto compounds, thioether compounds, sulfinic acid compounds, thiosulfonic acid compounds, thioamide compounds, urea compounds, selenourea compounds and the like. It is a thiourea compound, particularly preferably a nitrogen-containing heterocyclic compound, a mercapto compound, a thioether compound and a thiourea compound, and particularly preferably a nitrogen-containing heterocyclic compound.

In the present invention, the photographic emulsion which controls the photosensitive mechanism includes any of silver bromide, silver iodobromide, silver chlorobromide, silver iodide, silver iodochloride, silver iodobromochloride and silver chloride as silver halide. Although a halogen composition on the outermost surface of the emulsion may contain iodine of 0.1 mol% or more, more preferably 1 mol% or more, particularly preferably 5 mol% or more, a stronger multilayer adsorption structure can be constructed. The particle size distribution may be wide or narrow, but narrower is more preferable. The silver halide grains of a photographic emulsion are those having regular crystals such as cubic, octahedral, tetradecahedral, or rhombic dodecahedron, or irregular such as spherical, plate-like, etc. (Irregular) crystal form,
It may have a higher-order plane ((hkl) plane) or a mixture of grains of these crystal forms, but is preferably a tabular grain, and the tabular grain will be described in detail below. For particles with higher planes, see Journal of I
See pages 247 to 254 of Maging Science, Vol. 30 (1986). Further, the silver halide photographic emulsion used in the present invention may contain the above-mentioned silver halide grains singly or in combination.
The silver halide grains may have different phases between the inside and the surface layer, may have a multiphase structure having a bonding structure, may have a localized phase on the grain surface, or may have a uniform grain as a whole. It may consist of phases. They may be mixed. These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside a grain.

In the present invention, tabular silver halide grains having a halogen composition of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, and silver iodochloride are preferably used. The tabular grains preferably have a main surface of (100) or (111). Tabular grains having a (111) major surface, hereinafter referred to as (111) tabular, usually have triangular or hexagonal faces. Generally, the more uniform the distribution, the higher the proportion of tabular grains having more hexagonal faces. The hexagonal monodispersed flat plate is described in Japanese Patent Publication No. 5-61205.

Tabular grains having a (100) plane as a main surface,
The (100) flat plate also has a rectangular or square shape. In this emulsion, grains having an adjacent side ratio of less than 5: 1 are called tabular grains. In the case of silver chloride or tabular grains containing a large amount of silver chloride, (100) tabular grains originally have higher stability on the main surface than (111) tabular grains. In the case of a (111) flat plate, it is necessary to stabilize the (111) main surface.
-80660, JP-A-9-80656 and U.S. Pat. No. 5,298,388.

The silver chloride or the (111) flat plate having a high silver chloride content used in the present invention is disclosed in the following patents. U.S. Patent No. 4,414,306, U.S. Patent No. 4,400,463, U.S. Patent No. 4,713,323
No. 4,783,398; U.S. Pat.
No. 491, U.S. Pat. No. 4,983,508, U.S. Pat.
No. 804621, US Pat. No. 5,389,509, US Pat. No. 5,217,858, US Pat. No. 5,460,934.

The high silver bromide (111) tabular grains used in the present invention are described in the following patents. U.S. Pat. No. 4,425,425, U.S. Pat. No. 4,425,426,
U.S. Pat. No. 4,443,426; U.S. Pat. No. 4,439,520
No. 4,414,310; U.S. Pat.
048, U.S. Pat. No. 4,647,528, U.S. Pat.
No. 665012, U.S. Pat. No. 4,672,027, U.S. Pat. No. 4,678,745, U.S. Pat. No. 4,684,607,
U.S. Pat. No. 4,593,964, U.S. Pat.
6, U.S. Pat. No. 4,722,886, and U.S. Pat.
5617, U.S. Patent No. 4,755,456, U.S. Patent No. 4,806,461, U.S. Patent No. 4,801,522, U.S. Patent No. 4,835,322, U.S. Patent No. 4,839,268,
U.S. Pat. No. 4,914,014, U.S. Pat.
5, U.S. Pat. No. 4,977,074, U.S. Pat.
No. 5,350, U.S. Pat. No. 5,061,609, U.S. Pat. No. 5,061,616, U.S. Pat. No. 5,068,173, U.S. Pat. No. 5,132,203, U.S. Pat.
No. 5,334,469, U.S. Pat.
No. 495, US Pat. No. 5,358,840, US Pat.
372927.

The (100) flat plate used in the present invention is described in the following patents. US Patent 438
No. 6,156, US Pat. No. 5,275,930, US Pat. No. 5,292,632, US Pat. No. 5,314,798, US Pat. No. 5,320,938, US Pat. No. 5,319,635.
No. 5,356,764, European Patent No. 5699.
No. 71, EP 737887, JP-A-6-308
648, JP-A-9-5911.

The silver halide emulsion used in the present invention has a higher surface area / absorbing sensitizing dye disclosed in the present invention.
Tabular silver halide grains having a high volume ratio are preferred, and the aspect ratio is 2 or more (preferably 100 or less), preferably 5 or more and 80 or less, more preferably 8 or more and 80 or less. 50% (area)
The above emulsion is present, and the tabular grains have a thickness of 0.2
μm, preferably less than 0.1 μm,
More preferably, it is less than 0.07 μm. The following technology is applied to prepare such high aspect ratio and thin tabular grains. The tabular grains of the present invention desirably have a uniform dislocation dose distribution between grains. In the emulsion of the present invention, silver halide grains containing 10 or more dislocation lines per grain preferably occupy 100 to 50% (number) of all grains, more preferably 100 to 70%, particularly preferably 100 to 100%. Or 90%.

If it is less than 50%, it is not preferable in terms of homogeneity between particles.

In the present invention, when obtaining the ratio of the particles containing dislocation lines and the number of dislocation lines, it is preferable to directly observe the dislocation lines for at least 100 particles.
More preferably 200 particles or more, particularly preferably 300 particles
Observe for more than particles.

Gelatin is advantageously used as a protective colloid used in preparing the emulsion of the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives ;
Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylimidazole, etc. Can be used. Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci.
Photo. Japan. No. 16. P30 (196
Enzyme-treated gelatin as described in 6) may be used, and hydrolysates or enzymatic degradation products of gelatin can also be used. The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid.
The temperature of water washing can be selected according to the purpose, but is preferably selected in the range of 5 ° C to 50 ° C. The pH at the time of washing can be selected according to the purpose, but is preferably selected from 2 to 10. More preferably, it is in the range of 3 to 8. The pAg at the time of washing can be selected according to the purpose, but is preferably selected from 5 to 10. Noodle washing method, dialysis method using semi-permeable membrane,
The method can be selected from centrifugal separation, coagulation sedimentation, and ion exchange. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative, and the like can be selected.

When preparing the emulsion of the present invention, for example, during grain formation,
Deionization step, chemical sensitization, metal ion salt before coating
It is preferable to perform the above depending on the purpose. Dope particles
In the case of grain formation, modification or chemical sensitization of the grain surface
When used as an agent, add after grain formation and before completion of chemical sensitization
Is preferred. Doping the whole grain and the grain
Dope only the core part or only the shell part
You can also choose the law. For example, Mg, Ca, Sr, Ba, Al,
Sc, Y, La, Cr, Mn, Fe, Co, Ni, C
u, Zn, Ga, Ru, Rh, Pd, Re, Os, I
r, Pt, Au, Cd, Hg, Tl, In, Sn, P
b and Bi can be used. These metals are
Nitrate, acetate, nitrate, sulfate, phosphate, hydroxide, etc.
Or a 6-coordinate complex, a 4-coordinate complex, etc.
Any form of salt that can be added can be added. For example,
CdBr_Two , CdCl_Two , Cd (NO_Three)_Two , Pb (NO
_Three)_Two , Pb (CH_Three COO)_Two , K_Three [Fe (CN)
₆ ], (NH_Four)_Four [Fe (CN) ₆ ], K_Three IrCl
₆ , (NH_Four)_Three RhCl₆ , K_Four Ru (CN)₆ Is raised
Can be Halo, aquo, shea as ligands for coordination compounds
, Cyanate, thiocyanate, nitrosyl, thioni
You can choose from trosyl, oxo, and carbonyl
Wear. These may use only one kind of metal compound,
Two or more kinds may be used in combination.

The metal compound is preferably added after being dissolved in water or a suitable organic solvent such as methanol or acetone. In order to stabilize the solution, a method of adding an aqueous solution of hydrogen halide (eg, HCl, HBr) or an alkali halide (eg, KCl, NaCl, KBr, NaBr) can be used. Further, if necessary, an acid or an alkali may be added. The metal compound can be added to the reaction vessel before the formation of the particles or during the formation of the particles. A water-soluble silver salt (eg, AgNO ₃ ) or an aqueous alkali halide solution (eg, NaCl, K)
(Br, KI) and continuously during the formation of silver halide grains. Further, a solution independent of the water-soluble silver salt and alkali halide may be prepared and added continuously at an appropriate time during grain formation. It is also preferable to combine various addition methods.

In some cases, a method of adding a chalcogen compound during preparation of an emulsion as described in US Pat. No. 3,772,031 is also useful. In addition to S, Se, and Te, cyanide, thiocyanate, selenocyanic acid, carbonate, phosphate, and acetate may be present.

The silver halide grains of the present invention may be subjected to at least one of sulfur sensitization, selenium sensitization, gold sensitization, palladium sensitization or noble metal sensitization and reduction sensitization in any step of a silver halide emulsion production step. Can be applied. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type in which a chemical sensitizing nucleus is embedded in the grain, a type in which the chemical sensitizing nucleus is embedded in a position shallow from the grain surface, and a type in which a chemical sensitizing nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemical sensitization nucleus can be selected according to the purpose. Generally, the case where at least one type of chemical sensitization nucleus is formed near the surface is preferred. One of the chemical sensitizations that can be preferably performed in the present invention is chalcogen sensitization and noble metal sensitization alone or in combination, and is described by TH James, The Photographic Process, Fourth Edition, Macmillan. Published by the company
1977, (TH James, The Theo)
ry of the Photographic Pr
ocess, 4th ed, Macmillan, 19
77) can be carried out using active gelatin as described on pages 67-76, and can also be performed by Research Disclosure, 120, April 1974, 12008; Research Disclosure, 34, 1975, June.
Moon, 13452, U.S. Pat. Nos. 2,642,361, 3,297,446, and 3,772,031,
Nos. 3,857,711 and 3,901,714,
Nos. 4,266,018 and 3,904,4
No. 15 and pAg 5-10, pH 5-8 and temperature 30-30 as described in GB 1,315,755.
At 80 ° C., it can be sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of a plurality of these sensitizers. In the noble metal sensitization, noble metal salts such as gold, platinum, palladium, and iridium can be used, and among them, gold sensitization, palladium sensitization, and a combination of both are preferable. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, and gold selenide can be used. The palladium compound means a divalent palladium salt or a tetravalent salt. Preferred palladium compounds are represented by R ₂ PdX ₆ or R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom, and represents a chlorine, bromine or iodine atom.

Specifically, K_Two PdCl_Four , (NH_Four)_Two 
PdCl₆ , Na_Two PdCl_Four , (NH_Four)_Two PdCl
_Four , Li_Two PdCl_Four , Na_Two PdCl₆ Or K_Two P
dBr _Four Is preferred. Gold and palladium compounds
Is used in combination with thiocyanate or selenocyanate
Is preferred. Hypo and thiourea as sulfur sensitizers
Compound, rhodanine compound and US Patent No. 3,853
No. 7,711, No. 4,266,018 and No.
Sulfur-containing compounds described in 4,054,457
Can be used. In the presence of so-called chemical sensitization aids
Can also be chemically sensitized. Useful chemical sensitizer
For azaindene, azapyridazine and azapyrimidine
Fog in the process of chemical sensitization
Compounds known to be augmented are used. Chemistry
Examples of sensitizing aid modifiers are described in US Pat. No. 2,131,038.
No. 3,411,914, No. 3,554,75
No. 7, JP-A-58-126526 and the aforementioned duffin
"Photographic Emulsion Chemistry", pages 138-143.
You. The emulsion of the present invention is preferably used in combination with gold sensitization.
The preferred amount of the gold sensitizer is 1 per mole of silver halide.
× 10^-Four~ 1 × 10^-7Mole, more preferably
1 × 10^-Five~ 5 × 10^-7Is a mole. Palladium compound
Is preferably 1 × 10^-3From 5 × 10^-7It is. H
Preferred of ocyan compound or selenocyan compound
The range is 5 × 10^-2From 1 × 10^-6It is. Halo of the present invention
The preferred amount of sulfur sensitizer to be used for silver gemide grains is
1 × 10 per mole of silver halide^-Four~ 1 × 10^-7In mole
Yes, more preferably 1 × 10^-Five~ 5 × 10^-7Mole
It is. A preferred sensitizing method for the emulsion of the present invention is
There is Len sensitization. Known instability in selenium sensitization
Using a selenium compound, specifically, a colloidal metal
, Selenoureas (eg, N, N-dimethylselene)
Nourea, N, N-diethylselenourea), selenoketone
Use of selenium compounds such as selenium and selenoamides
Can be. Selenium sensitization is sulfur sensitization or precious metal sensitization
Or it is better to use in combination with both.
is there.

During the grain formation of the silver halide emulsion of the present invention,
It is preferable to perform reduction sensitization after grain formation and before or during chemical sensitization, or after chemical sensitization. Here, reduction sensitization refers to a method of adding a reduction sensitizer to a silver halide emulsion, a method of growing or ripening in an atmosphere of a low pAg of pAg 1 to 7 called silver ripening, or a method of pH 8 to 10 called high pH ripening. Either a method of growing or ripening in a high pH atmosphere of 11 can be selected. Also, two or more methods can be used in combination. The method of adding a reduction sensitizer is a preferable method since the level of reduction sensitization can be finely adjusted. Examples of the reduction sensitizer include stannous salts, ascorbic acid and derivatives thereof, amines and polyamines, hydrazine derivatives, formamidine sulfinic acid,
Silane compounds and borane compounds are known. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, and two or more compounds can be used in combination. As reduction sensitizers, stannous chloride, thiourea dioxide,
Dimethylamine borane, ascorbic acid and its derivatives are preferred compounds. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but an appropriate range is from 10 ^-7 to 10 ^-3 mol per mol of silver halide. The reduction sensitizer is dissolved in water or an organic solvent such as alcohols, glycols, ketones, esters, and amides and added during grain growth. It may be added to the reaction vessel in advance, but a method of adding at an appropriate time during the particle growth is preferable. Further, a reduction sensitizer may be added in advance to the water solubility of a water-soluble silver salt or a water-soluble alkali halide, and silver halide grains may be precipitated using these aqueous solutions. It is also a preferred method to add the solution of the reduction sensitizer several times as the grains grow, or to add them continuously for a long time.

It is preferable to use an oxidizing agent for silver during the production process of the emulsion of the present invention. The oxidizing agent for silver is
A compound that acts on metallic silver to convert it into silver ions. In particular, a compound that converts extremely fine silver grains by-produced during the formation process of silver halide grains and the chemical sensitization process into silver ions is effective. The silver ion generated here may form a water-insoluble silver salt such as silver halide, silver sulfide or silver selenide, or a water-soluble silver salt such as silver nitrate. May be formed. The oxidizing agent for silver may be inorganic or organic. As the inorganic oxidizing agent, for example, ozone, hydrogen peroxide and its adduct (eg, NaBO ₂
・ H ₂ O ₂ .3H ₂ O, 2NaCO ₃ .3H ₂ O ₂ , N
_{a 4 P 2 O 7 · 2H} 2 O 2, 2Na 2 SO 4 · H 2 O 2
2H ₂ O), peroxy acid salt (for example, K ₂ S ₂ O)
₈ , K ₂ C ₂ O ₆ , K ₂ P ₂ O ₈ ), peroxy complex compounds (for example, K ₂ [Ti (O ₂ ) C ₂ O ₄ ] · 3H ₂
O, 4K ₂ SO ₄ .Ti (O ₂ ) OH.SO ₄ .2H ₂
O, Na ₃ [VO (O ₂ ) (C ₂ H ₄ ) ₂ ] · 6H ₂ O),
Oxygenates such as permanganate (eg, KMnO ₄ ), chromate (eg, K ₂ Cr ₂ O ₇ ), halogen elements such as iodine and bromine, perhalates (eg, periodate) Potassium), high valent metal salts (eg, potassium hexacyanoferrate) and thiosulfonates.

Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds which release active halogen (for example, N-
Bromsuccinimide, chloramine T, chloramine B)
Is given as an example.

Preferred oxidizing agents of the present invention are inorganic oxidizing agents such as ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfonates, and organic oxidizing agents such as quinones.
It is a preferred embodiment to use the above-described reduction sensitization and an oxidizing agent for silver in combination. The method can be selected from a method of performing reduction sensitization after using an oxidizing agent, a method reverse thereto, or a method of coexisting both methods. These methods can be selectively used in both the grain formation step and the chemical sensitization step.

The photographic emulsion used in the present invention may contain a compound other than the above-mentioned silver halide-adsorbing compound in order to prevent fog during the production process, storage or photographic processing of the photographic material, or to stabilize photographic performance. Can also be included.

The light-sensitive material produced by using the silver halide emulsion obtained in the present invention may be any light-sensitive material as long as it is a silver halide photographic light-sensitive material. Various layer configurations and arrangements can be selected according to the purpose.

The above-mentioned various additives are used in the light-sensitive material according to the present invention. In addition, various additives can be used according to the purpose.

These additives are described in more detail in Research Disclosure Item 17643 (1978).
Item 18716 (January 1979)
Jan.) and Item 308119 (December 1989), and the relevant portions are summarized in the table below.

Additive type RD17643 RD18716 RD308119 1 Chemical sensitizer page 23, page 648, right column, page 996 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, page 23-24, page 648, right column to 996, right to 998 right Super strong Sensitizer Page 649 Right column 4 Brightener 24 Page 647 Page Right column 998 Right 5 Antifoggant, Page 24 to 25 Page 649 Right column 998 Right to 1000 Right and Stabilizer 6 Light absorber, 25 to 26 649 Page right column to 1003 left to 1003 right Filter dye, page 650 Left column UV absorber 7 Stain inhibitor page 25 right column 650 left to right column 1002 right 8 Dye image stabilizer 25 page 1002 right 9 Hardener 26 page 651 Page left column 1004 right to 1005 left 10 Binder page 26 Same as above 1003 right to 1004 right 11 Plasticizer, lubricant 27 page 650 Page right column 1006 left to 1006 right 12 Coating aid, page 26 to 27 Same as above 1005 left 1006 left Surfactant 13 Static page 27 Same as above 1006 right to 1007 left Inhibitor 14 matting agent 1008 left to 1009 left

When the light-sensitive material used in the present invention is a color photographic light-sensitive material, various color couplers can be used. Specific examples thereof are described in Research Disclosure No. No. 17643, VII-CG and No. 307
105, VII-CG. The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods. The present invention can be applied to various color light-sensitive materials. For example, color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers can be mentioned as typical examples. The present invention can be particularly preferably used for a color duplication film.

Suitable supports that can be used in the present invention are described, for example, in RD. No. No. 17643, page 28;
No. 18716, from the right column on page 647 to the left column on page 648; 307105, page 879.

The color photographic light-sensitive material according to the present invention is prepared according to the RD. No. No. 17643, pages 28 to 29;
No. 18716, page 651, left column to right column; 30
The development can be carried out by a usual method described on pages 880 to 881 of No. 7105. In the silver halide color photographic light-sensitive material of the present invention, a color developing agent may be incorporated for the purpose of simplifying and speeding up the processing.

The silver halide light-sensitive material of the present invention comprises
It can also be applied to photothermographic materials.

Further, the silver halide color photographic light-sensitive material of the present invention is more effective when it is applied to a film unit with a lens, and is effective.

The present invention can be preferably used for a diffusion transfer photographic material such as a color diffusion transfer photographic film unit.

[0157]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Example 1 (Preparation of seed emulsion a) KBr 0.017 g, average molecular weight 2
Aqueous solution 11 containing 0.4 g of 0000 oxidized gelatin
64 ml was kept at 35 ° C. and stirred. AgNO ₃ (1.6
g) An aqueous solution, an aqueous KBr solution, and an aqueous solution of oxidized gelatin (2.1 g) having an average molecular weight of 20,000 were added over 48 seconds by a triple jet method. At this time, the silver potential was kept at 13 mV with respect to the saturated calomel electrode. After an aqueous KBr solution was added to adjust the silver potential to −66 mV, the temperature was raised to 60 ° C. 21 g of succinated gelatin having an average molecular weight of 100,000
Was added, and an aqueous solution of NaCl (5.1 g) was added. An aqueous solution of AgNO ₃ (206.3 g) and an aqueous solution of KBr were added over 61 minutes while accelerating the flow rate by the double jet method. At this time, the silver potential was kept at -44 mV with respect to the saturated calomel electrode. After desalting, the average molecular weight is 100
000 succinated gelatin and pH 5 at 40 ° C.
The pAg was adjusted to 8, and a seed emulsion was prepared. This seed emulsion contains 1 mol of Ag and 8 gelatin per kg of emulsion.
0 g, tabular grains having an average equivalent circle diameter of 1.46 μm, a coefficient of variation of equivalent circle diameter of 28%, an average thickness of 0.046 μm, and an average aspect ratio of 32.

(Formation of core) 134 g of the seed emulsion a was prepared.
Succinated KBr 1.9 g, average molecular weight 100000
Keep 1200 ml of aqueous solution containing 22 g of rat at 75 ° C
Stirred. AgNO _Three (43.9 g) aqueous solution and KBr water
Solution and an aqueous solution of gelatin having a molecular weight of 20,000
-43570 Magnetic coupling induction type stirrer
25 minutes mixing just before addition in another chamber with
Added over time. At this time, the silver potential is changed to a saturated calomel electrode.
-40 mV.

(Formation of First Shell) After the formation of the core particles, an aqueous solution of AgNO ₃ (43.9 g), an aqueous solution of KBr, and an aqueous solution of gelatin having a molecular weight of 20,000 were mixed immediately before the addition in another chamber in the same manner as above to form a solution. Added over minutes. At this time, the silver potential was set to −40 with respect to the saturated calomel electrode.
mV.

(Formation of Second Shell) After the formation of the first shell, an aqueous solution of AgNO ₃ (42.6 g), an aqueous solution of KBr, and an aqueous solution of gelatin having a molecular weight of 20,000 were mixed immediately before addition in another chamber of the same type. Added over 17 minutes. At this time, the silver potential was set to -20 with respect to the saturated calomel electrode.
mV. Thereafter, the temperature was lowered to 55 ° C.

(Formation of Third Shell) After the formation of the second shell, the silver potential was adjusted to -55 mV, and AgNO ₃ (7.
1 g) aqueous solution, KI (6.9 g) aqueous solution and molecular weight 200
The gelatin aqueous solution of No. 00 was mixed immediately before the addition in another chamber as above and added over 5 minutes.

(Formation of Fourth Shell) After the formation of the third shell, an aqueous solution of AgNO ₃ (66.4 g) and an aqueous solution of KBr were added at a constant flow rate over 30 minutes by a double jet method. On the way, iridium potassium hexachloride and yellow blood salt were added. At this time, the silver potential is set at 30 with respect to the saturated calomel electrode.
mV. Perform normal water washing, add gelatin,
PH was adjusted to 5.8 and pAg to 8.8 at 40 ° C. This emulsion was designated as emulsion b. Emulsion b had an average equivalent circle diameter of 3.3 μm,
Coefficient of variation of equivalent circle diameter 21%, average thickness 0.090μm,
The tabular grains had an average aspect ratio of 37. Further, 70% or more of the total projected area has a circle equivalent diameter of 3.3 μ or more and a thickness of 0.3 μm.
Occupied by tabular grains of 090 μm or less. One layer saturation coverage of when the dye occupation area as 80 Å ² 1.4
It was 5 × 10 ⁻³ mol / mol Ag.

Comparative Example 1 Emulsion b was heated to 56 ° C., and D-1 was changed to 2.4 × 10 ^-4 mo.
1 / mol Ag and D-4 at 9.6 × 10 ^-4 mol / mo
After the addition of 1Ag, C-5, potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were added for optimal chemical sensitization. Further D-
2.5 × 10 ^-4 mol / mol Ag was added and stirred for 60 minutes. However, D-1 and D-4 were added to the emulsion b in a methanol solution.

[0165]

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Comparative Example 2 Emulsion b was heated to 56 ° C., and D-1 was changed to 2.4 × 10 ⁻⁴ mo.
1 / mol Ag and D-4 at 9.6 × 10 ^-4 mol / mo
After the addition of 1Ag, C-5, potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were added for optimal chemical sensitization. Further D-
2.5 × 10 ⁻⁴ mol / mol Ag was added thereto and stirred for 10 minutes. Thereafter, D-6 was added at 2.0 × 10 ⁻³ mol / m.
olAg was added and the mixture was further stirred for 60 minutes. However, D-
1, D-2, and D-6 were added to Emulsion b as a methanol solution. Comparative Example 3 Emulsion b was heated to 56 ° C., and D-1 was changed to 2.4 × 10 ⁻⁴ mo.
1 / mol Ag and D-4 at 9.6 × 10 ^-4 mol / mo
After the addition of 1Ag, C-5, potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were added for optimal chemical sensitization. Further D-
2.5 × 10 ^-4 mol / mol Ag was added and stirred for 60 minutes. D-1 and D-4 were added to Emulsion b as phenoxyethanol oil droplet dispersions. Invention 1 Emulsion b was heated to 56 ° C., and D-1 was changed to 2.4 × 10 ⁻⁴ mo.
1 / mol Ag and D-4 at 9.6 × 10 ^-4 mol / mo
After the addition of 1Ag, C-5, potassium thiocyanate, chloroauric acid, sodium thiosulfate and N, N-dimethylselenourea were added for optimal chemical sensitization. Further D-
2.5 × 10 ⁻⁴ mol / mol Ag was added thereto and stirred for 10 minutes. Thereafter, D-6 was added at 2.0 × 10 ⁻³ mol / m.
olAg was added and the mixture was further stirred for 60 minutes. D-1, D-
2, and D-6 were added to emulsion b as a phenoxyethanol oil droplet dispersion. A phenoxyethanol oil droplet dispersion of a sensitizing dye was produced by the following method. That is,
Dissolve 0.4 g of sensitizing dye in 5 ml of phenoxyethanol,
A solution containing 45 ml of distilled water was added at 50 ° C.
The mixture was stirred at 12000 rpm for 20 minutes using a blade. 50 ml of an aqueous gelatin solution was added to the resulting oil-in-water dispersion to obtain a phenoxyethanol oil-drop dispersion of a sensitizing dye.

The light absorption intensity of the emulsion obtained by adding the sensitizing dye was measured. The temperature of the emulsion was kept at 40 ° C., and the light absorption intensity was measured one hour after the addition of the coupler oil droplet dispersion. The coupler oil droplet dispersion was produced by the following method. Couplers, high-boiling organic solvents, surfactants, low-boiling organic solvents, and other additive solvents,
Mix an aqueous solution of gelatin, stir, emulsify and disperse,
Prepared by removing low boiling organic solvents by evaporation. The chemical formula of the coupler used is shown below.

[0168]

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[0169]

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[0170]

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[0171]

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The measurement of the light absorption intensity per unit area is
Apply the thin emulsion to a glass slide
Using Ice Microscope MSP65
The transmission spectrum and the reflection of each particle are
The emission spectrum was measured to determine the absorption spectrum. Transparent
The hyperspectral reference is the particle-free part
And the reflection spectrum is a silicon camera whose reflectance is known.
The carbide was measured and used as a reference. Measurement part is diameter
1μm circular aperture, with aperture on particle outline
Adjust the position so that the char section does not overlap and 14000
cm^-1(714 nm) to 28000 cm^-1(357n
Transmission spectrum and reflection spectrum in the wave number range up to m)
1-T (transmittance) -R (reflectance)
The absorption spectrum was determined as A. Silver halide absorption
Is subtracted to obtain an absorption rate A ′, and −Log (1-A ′) is
Wave number (cm^-1), Halving the integrated value
The light absorption intensity per surface area was used. Integration range is 1400
0cm^-1From 28000cm ^-1Up to. At this time,
The source is a tungsten lamp and the light source voltage is 8V
Was. Primary to minimize dye damage from light irradiation
Using the monochromator on the side, the wavelength interval is 2 nm,
The cut width was set to 2.5 nm. Light about 200 particles
The absorption intensity was determined.

Table 1 shows the results.

[0174]

[Table 1]

It was found that the addition of the sensitizing dye as an oil droplet dispersion significantly improved the stability of the multilayer adsorption system to the coupler oil droplet dispersion.

Gelatin hardeners were added to the emulsions obtained by adding sensitizing dyes as in Comparative Examples 1, 2, and 3, and in the present invention 1,
And a coating aid, and the coated silver amount was 3.0 g-Ag / m.
At ^2, on a cellulose acetate film support, and simultaneous coating with a gelatin protective layer, respectively the samples 101 and 102, was 103 or 104,. Further, to the emulsions obtained by adding the sensitizing dyes as in Comparative Examples 1, 2, and 3, or the present invention 1, the above-described coupler oil droplet dispersion was added, and after one hour had passed. Samples obtained by coating the emulsion in the same manner as above were designated as Samples 105, 106, 107 and 108, respectively. The absorption intensity of the obtained film was measured with a spectrophotometer U3500 manufactured by Hitachi. 14000cm
^-1 (714 nm) to 28000 cm ^-1 (357 nm)
The absorption spectrum was determined as the absorption rate A in the wave number range up to and the absorption of silver halide was subtracted to obtain the absorption rate A ′, and the value obtained by integrating −Log (1-A ′) with the wave number (cm ⁻¹ ) was obtained. The light absorption intensity of the coated film was used. The resulting film was exposed to a tungsten bulb (color temperature 2854K) for 1 second through a continuous wedge color filter. Using a Fuji gelatin filter SC-50 (manufactured by FUJIFILM Corporation) for minus blue exposure which excites the dye side as a color filter, light of 500 nm or less was blocked and the sample was irradiated. The exposed sample was the following surface developer MA
Development was performed at 20 ° C. for 10 minutes using A-1.

Surface developer MAA-1 formulation Metol 2.5 g L-ascorbic acid 10 g Navox (Fuji Film Co., Ltd.) 35 g Potassium bromide 1 g Water is added to 1 liter pH 9.8

After development, fixing was performed at 20 ° C. with the following fixing solution. Fixer formulation Ammonium thiosulfate 170 g Sodium sulfite (anhydrous) 15 g Boric acid 7 g Glacial acetic acid 15 mL Potassium alum 20 g Ethylenediaminetetraacetic acid 0.1 g Tartaric acid 3.5 g 1 liter with added water Measured optical density with Fuji automatic densitometer The sensitivity was represented by the reciprocal of the amount of light required to provide an optical density of +0.2, and the sensitivity of Comparative Example 1 was expressed as 100.

The results are shown in Table 2. It was found that by adding the sensitizing dye as an oil droplet dispersion, the stability of the multilayer adsorption system to the coupler oil droplet dispersion was remarkably improved even in the coated film.

[0180]

[Table 2]

Example 2 A tabular silver iodobromide emulsion was prepared in the same manner as in Emulsion D of Example 5 of JP-A-8-29904 to prepare Emulsion c. The multilayer color photosensitive material was prepared in the same manner as in Sample 5 of Example 5 of JP-A-8-29904. Sample 10 of Example 5 of JP-A-8-29904
The emulsion L of the twelfth layer in Example 1 was replaced with emulsion c, and ExS-7
Was changed to sensitizing dye D-14, and a sample in which each dye was added in an amount of 3 × 10 ⁻⁴ mol per mol of silver halide as a methanol solution and a solid fine dispersion was used as samples 109 and 110 for comparison, respectively. And Further, the emulsion L of the twelfth layer in the sample 101 of Example 5 of JP-A-8-29904 was replaced with the emulsion c, and ExS-7 was changed to sensitizing dyes D-14, D-16 and D-32. In addition, a sample in which each dye was added as a methanol solution at 3 × 10 ^-4 mol per mol of silver halide was designated as Sample 111 for comparison. Further, the emulsion L of the twelfth layer in the sample 101 of Example 5 of JP-A-8-29904 was replaced with the emulsion c, and ExS-7 was changed to sensitizing dyes D-14, D-16, and D-32. A sample to which 3 × 10 ⁻⁴ mol of each dye was added as a solid dispersion per mol of silver halide was designated as Sample 112 of the present invention. A solid fine dispersion of the sensitizing dye was produced by the following method. That is, 0.5 g of the sensitizing dye was added to 50 parts of distilled water.
The resulting suspension was stirred at 12,000 rpm for 20 minutes at 50 ° C. using a #solver blade. 50 ml of an aqueous gelatin solution was added to the obtained solid dispersion to obtain a solid fine dispersion of a sensitizing dye. The light absorption intensity of the obtained coated film was measured in the same manner as in Example 1. The sensitivity was determined by measuring the yellow color density of the sample. The results are shown in Table 3. It was found that the addition of the sensitizing dye in the form of a fine solid dispersion makes it difficult for the absorption intensity of the multilayer adsorption dye to change in the coated film, and the stability of the multilayer adsorption system is remarkably improved.

[0182]

[Table 3]

[0183]

From the examples of the present invention, a silver halide emulsion is obtained in which the spectral absorption of the emulsion in which the sensitizing dye is adsorbed in multiple layers, the stability in the dissolved state or the dispersion to the coupler oil droplets is remarkably improved. be able to.

Claims (12)

[Claims] 2. The method according to claim 1, wherein the spectral absorption maximum wavelength is less than 500 nm and the light absorption intensity is 60 or more, or the spectral absorption maximum wavelength is 500.
A silver halide photographic emulsion comprising a silver halide photographic emulsion containing silver halide grains having a light absorption intensity of 100 nm or more and a sensitizing dye added in a form other than a solution using an organic solvent. 2. The silver halide photographic emulsion according to claim 1, wherein the sensitizing dye is added in the form of a solid fine dispersion. 3. The silver halide emulsion according to claim 2, wherein the sensitizing dye is added in the form of a solid fine dispersion in which the sensitizing dye is finely dispersed using a surfactant. 4. The silver halide photographic emulsion according to claim 1, wherein the sensitizing dye is added in the form of an oil droplet dispersion in which a solution of the sensitizing dye is finely dispersed in water. 5. The silver halide photographic emulsion according to claim 4, wherein the sensitizing dye is added in the form of an oil droplet dispersion in which the sensitizing dye is finely dispersed using a surfactant. 6. A halogenated silver halide emulsion according to claim 1, which contains a silver halide photographic emulsion in which a sensitizing dye is adsorbed on the surface of the silver halide grains in a multilayer manner. Silver photographic emulsion. 7. The maximum value of the spectral absorption by the sensitizing dye is defined as Am
7. The silver halide according to claim 1, wherein the wavelength interval between the shortest wavelength and the longest wavelength indicating 50% of Amax is 120 nm or less when ax is set. Photographic emulsion. 8. The maximum value of the spectral sensitivity of the sensitizing dye is defined as Smax
7. The silver halide photograph according to claim 1, wherein the wavelength interval between the shortest wavelength and the longest wavelength which indicates 50% of Smax is 120 nm or less. emulsion. 9. The halogenated silver halide emulsion according to claim 1, wherein the silver halide photographic emulsion contains a dye having at least one aromatic group. Silver photographic emulsion. 10. An emulsion in which tabular grains having an aspect ratio of 2 or more are present in an amount of 50% or more (area) of all silver halide grains in the emulsion.
10. The silver halide photographic emulsion according to 5, 6, 7, 8 or 9. 11. The silver halide photograph according to claim 6, wherein the excitation energy of the second-layer dye is transferred to the first-layer dye at an efficiency of 10% or more. emulsion. 12. The dye according to claim 6, wherein both the first-layer dye and the second-layer dye exhibit J-band absorption.
9. The silver halide photographic emulsion according to 9, 10, 11 or 12.